Luminescent-polymer composition

ABSTRACT

A light-emitting polymer composition comprising a light-emitting polymer and an ion pair, wherein the ion pair has a negative ion of a specific structure in which one group 13 atom and is bonding to an aryl group having an electron-withdrawing group, or a heterocyclic group having an electron-withdrawing group, directly or through a connecting group; or two or more group 13 atoms, and all the atoms are respectively bonding to an aryl group having an electron-withdrawing group, or a heterocyclic group having an electron-withdrawing group, directly or through a connecting group.

TECHNICAL FIELD

The present invention relates to a light-emitting polymer composition, alight-emitting polymer solution composition, and a polymerlight-emitting device (polymer LED) using thereof.

BACKGROUND TECHNOLOGY

Unlike a low molecular weight material, a high molecular weightlight-emitting material (light-emitting polymer) is soluble in asolvent, can form a light emitting layer of a light-emitting device by acoating method, and thus coincide with the demand of large areaformation of a device. For this reason, in recent-years, various polymerlight-emitting materials are proposed (for example, Advanced MaterialsVol. 12 1737-1750 (2000)).

Meanwhile, it is desired for a light-emitting device to have long-life,that is, small deterioration of luminance by driving.

However, when a light-emitting polymer is used as a material for a lightemitting layer of light-emitting device, the life-time of the device hasbeen not yet satisfactory.

DISCLOSURE OF THE INVENTION

The object of the present invention is to provide a composition whichcan give a long-life light-emitting device, when used for a lightemitting layer of light-emitting device.

As the result of intensive studies in order to solve the above problems,the present inventors found a composition comprising a light-emittingpolymer, and an ion pair which contains, as the negative ion, a group 13atom connecting with an aryl group having an electron-withdrawing group,or a monovalent heterocyclic group having an electron-withdrawing groupdirectly or through a connecting group; or contains two or more group 13atoms, all of the atoms, each respectively being connected with an arylgroup having an electron-withdrawing group, or a monovalent heterocyclicgroup having an electron-withdrawing group directly or through aconnecting group; and found that when said composition is used as amaterial for light emitting device, the life-time of said device becomelong, and reached to the present invention.

That is, the present invention provides a light-emitting polymercomposition containing a light-emitting polymer and an ion pair, and thenegative ion of the ion pair is represented by the below formula (1a),(1b), (2), or (3).

(wherein, Y¹ represents a group 13 atom; Ar¹ represents an aryl grouphaving an electron-withdrawing group, or a monovalent heterocyclic grouphaving an electron-withdrawing group; Q¹ represents an oxygen atom or adirect bond; X¹ represent a halogen atom, alkyl group, alkyloxy group,alkylthio group, aryl group, aryloxy group, arylthio group, arylalkylgroup, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynylgroup, arylalkenyl group, arylalkynyl group, substituted silyloxy group,substituted silylthio group, substituted silylamino group, substitutedamino group, amide group, acid imide group, acyloxy group, monovalentheterocyclic group, heteroaryloxy group, heteroarylthio group, cyanogroup, or nitro group; a represents an integer of 1-3, k represents aninteger of 1-4, V¹ represents a group 16 atom, divalent aliphatichydrocarbon group, divalent aromatic hydrocarbon group, bidentateheterocyclic group, —C≡N—, —N═N═N—, or a direct bond; b represents aninteger of 2-6; and Z¹ represents -M′(=O)p- (wherein, M′ represents anatom of group 3, group 4, group 5, group 6, group 7, group 8, group 9,group 10, group 11, group 12, group 13, group 14, group 15, group 16, orgroup 17; and p represents an integer of 0-2), or Z¹ represents ab-valent aliphatic hydrocarbon group, a b-valent aromatic hydrocarbongroup, a bidentate heterocyclic group, —C≡N—, —N═N═N—, —NH—, —NH₂—,—OH—, or a direct bond. However, when b=2, Z¹ is —C≡N—, —N═N═N—, —NH—,—NH₂—, or —OH—; Z¹ and V¹ are different from each other, and when Q¹ andAr¹ exist in plural, they may be the same or different from each other;a plurality of V¹ may be the same or different; and c represents aninteger of 1-6),

(wherein, Y² represents a group 13 atom; Ar² represents an aryl grouphaving an electron-withdrawing group, or a monovalent heterocyclic grouphaving an electron-withdrawing group; Q² represents an oxygen atom or adirect bond; X² represent a halogen atom, alkyl group, alkyloxy group,alkylthio group, aryl group, aryloxy group, arylthio group, arylalkylgroup, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynylgroup, arylalkenyl group, arylalkynyl group, substituted silyl oxygroup, substituted silylthio group, substituted silylamino group,substituted amino group, amide group, acid imide group, acyloxy group,monovalent heterocyclic group, heteroaryloxy group, heteroarylthiogroup, cyano group, or nitro group; d and d′ each independentlyrepresent 1 or 2; V² represents a group 16 atom, divalent aliphatichydrocarbon group, divalent aromatic hydrocarbon group, bidentateheterocyclic group, —C≡N— or —N═N—; a plurality of Y², Ar², Q² and V²may be the same or different; when X² exists in plural, they may be thesame or different; and e represents an integer of 1-6),

(wherein, Y³ represents a group 13 atom; Ar³ represents an aryl grouphaving an electron-withdrawing group, or a monovalent heterocyclic grouphaving an electron-withdrawing group; Q³ represents an oxygen atom or adirect bond; V³ represents a group 16 atom, divalent aliphatichydrocarbon group, divalent aromatic hydrocarbon group, bidentateheterocyclic group, —C ≡N—, or —N═N—; a plurality of Y³, Ar³, Q³ and V³espectively may be the same or different; and f represents an integer of1-6).

In addition to the above light-emitting polymer composition, the presentinvention relates to a light-emitting polymer solution composition whichfurther contains a solvent.

BEST MODE FOR CARRYING OUT THE INVENTION

As for the ion pair used for the composition of the present invention,the negative ion is represented by the above formula (1a), (1b), (2), or(3).

Y¹ in formulas (1 a) and (1b) represents a group 13 atom, preferably,boron, aluminum and gallium, and more preferably, boron.

Ar¹ in formulas (1 a) and (1b) represents an aryl group having anelectron-withdrawing group, or a monovalent heterocyclic group having anelectron-withdrawing group.

The electron-withdrawing group means an atom or atomic group whichwithdraw electron by resonance effect or inductive effect, and examplesthereof include a halogen atom, nitro group, nitroso group, cyano group,acyl group, carboxyl group, alkyloxy carbonyl group, aryloxy carbonylgroup, arylalkyloxy carbonyl group, heteroaryloxy carbonyl group,perfluoroalkyl group, etc.

In the electron-withdrawing group, as the halogen atoms, a fluorineatom, a chlorine atom, a bromine atom, and an iodine atom areexemplified, and a fluorine atom is preferable.

Acyl group has usually about 2 to 20 carbon atoms, and concrete examplesthereof include acetyl group, propionyl group, butyryl group, isobutyrylgroup, pivaloyl group, benzoyl group, the trifluoroacetyl group,pentafluorobenzoyl group, etc.

Alkyloxy carbonyl group has usually about 2 to 20 carbon atoms, andconcrete examples thereof include methoxycarbonyl group, ethoxycarbonylgroup, propyloxycarbonyl group, i-propyloxycarbonyl group,butoxycarbonyl group, i-butoxy carbonyl group, t-butoxycarbonyl group,pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonylgroup, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxy carbonyl group,3,7-dimethyloctyloxycarbonyl group, lauryl oxycarbonyl group,trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group,perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group,perfluorooctyloxy carbonyl group, etc.

Aryloxy carbonyl group has usually about 7 to 60 carbon atoms, andconcrete examples thereof include a phenoxycarbonyl group, C₁-C₁₂alkyloxyphenoxycarbonyl group, C₁-C₁₂ alkylphenoxy carbonyl group,1-naphtyloxycarbonyl group, 2-naphtyloxy carbonyl group,pentafluorophenyloxycarbonyl group, etc.

Arylalkyloxycarbonyl group has usually about 8 to 60 carbon atoms, andconcrete examples thereof include phenyl-C₁-C₁₂ alkyloxycarbonyl group,C₁-C₁₂ alkyloxyphenyl-C₁-C₁₂ alkyloxy carbonyl group, C₁-C₁₂alkylphenyl-C₁-C₁₂ alkyloxycarbonyl group, 1-naphtyl-C₁-C₁₂alkyloxycarbonyl group, 2-naphtyl-C₁-C₁₂ alkyloxy carbonyl group, etc.

Heteroaryloxycarbonyl group (a group represented by Q⁴-O(C═O)— and Q⁴represent a monovalent heterocyclic group) has usually about 2 to 60carbon atoms, and concrete examples thereof include thienyloxy carbonylgroup, C₁-C₁₂ alkylthienyl oxy carbonyl group, pyroryloxycarbonyl group,furyloxy carbonyl group, pyridyloxycarbonyl group, C₁-C₁₂ alkylpyridyloxycarbonyl group, imidazolyloxycarbonyl group, pyrazolyloxy carbonylgroup, triazolyloxycarbonyl group, oxazolyloxy carbonyl group,thiazoleoxycarbonyl group, thiadiazoleoxy carbonyl group, etc.

Perfluoroalkyl group means a linear, branched or cyclic alkyl group inwhich all the hydrogen atoms on the alkyl group are replaced byfluorines, and has usually about 1 to 20 carbon atoms. Concrete examplesthereof include trifluoromethyl group, perfluoroethyl group,perfluoropropyl group, hepta fluoro-i-propyl group, perfluorobutylgroup, trifluoro-i-butyl group, 1,1-bistrifluoromethyl-2,2,2-trifluoroethyl group, perfluoropentyl group, perfluorohexylgroup, perfluorocyclohexyl group, perfluoro heptyl group, perfluorooctylgroup, perfluorononyl group, perfluorodecyl group, perfluoro laurylgroup, etc.

Next, in Ar¹ of formula (1a) and (1b), the aryl group having anelectron-withdrawing group, the monovalent heterocyclic group having anelectron-withdrawing group, an aryloxy group having anelectron-withdrawing group, and a monovalent hetero aryloxy group havingan electron-withdrawing group will be explained.

Aryl group having an electron-withdrawing group has usually about 6 to60 carbon atoms, and concrete examples thereof include a phenyl group,C₁-C₁₂ alkyloxy phenyl group (C₁-C₁₂ shows the number of carbon atoms1-12. hereafter the same), C₁-C₁₂ alkylphenyl group, 1-naphtyl group,2-naphtyl group, etc., which are substituted with one or more of theabove electron-withdrawing groups.

Monovalent heterocyclic group having an electron-withdrawing group hasusually about 2 to 60 carbon atoms, and concrete examples thereofinclude thienyl group, C₁-C₁₂ alkylthienyl group, pyroryl group, furylgroup, pyridyl group, C₁-C₁₂ alkylpyridyl group, imidazolyl group,pyrazolyl group, triazolyl group, oxazolyl group, thiazole group,thiadiazole group, etc., which are substituted with one or more of theabove electron-withdrawing groups.

Concrete examples of Ar¹ include the following groups (I)-(V).(I) Aryl Group Having an Electron-Withdrawing Group:

(II) Monovalent Heterocyclic Group Having an Electron-Withdrawing Group:

(III) Aryl Group Having a Fluorine Atom or Trifluoromethyl Group as theElectron-Withdrawing Group:

(IV) Monovalent Heterocyclic Group Having a Fluorine Atom orTrifluoromethyl Group as the Electron-Withdrawing Group:

(V) Perfluoroaryl Group, Perfluoro Aryloxy Group:

Examples of the perfluoroaryl group include pentafluoro phenyl group,heptafluoro-1-naphtyl group, hepta fluoro-2-naphtyl group,nonafluoro-1-biphenyl group, nonafluoro-2-biphenyl group,nonafluoro-1-anthracenyl group, nonafluoro-2-anthracenyl group, andnonafluoro-9-anthracenyl group.

As the aryl group having an electron-withdrawing group, and monovalentheterocyclic group having an electron-withdrawing group, those having afluorine atom or trifluoromethyl group are preferable (the aboveformulas (III), (IV), and (V)), and perfluoroaryl group (the aboveformula (V)) is more preferable.

Q¹ in formulas (1a) and (1b) represents an oxygen atom or a direct bond.

X¹ in formula (1a) and (1b) represents a halogen atom, alkyl group,alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthiogroup, arylalkyl group, the arylalkyloxy group, arylalkylthio group,alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group,substituted silyloxy group, substituted silylthio group, substitutedsilylamino group, substituted amino group, amide group, acidimide group,acyloxy group, monovalent heterocyclic group, heteroaryloxy group,heteroarylthio group, cyano group, or nitro group.

As the halogen atom in X¹, fluorine, chlorine, bromine, and iodine areexemplified.

The alkyl group may be any of linear, branched or cyclic, and may haveone or more substituents. The number of carbon atoms is usually about 1to 20, and specific examples thereof include methyl group, ethyl group,propyl group, i-propyl group, butyl group, and i-butyl group, t-butylgroup, pentyl group, hexyl group, cyclohexyl group, heptyl group, octylgroup, 2-ethyl hexyl group, nonyl group, decyl group, 3,7-dimethyloctylgroup, lauryl group, trifluoromethyl group, pentafluoroethyl group,perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, etc.

The alkyloxy group may be any of linear, branched or cyclic, and mayhave one or more substituents. The number of carbon atoms is usuallyabout 1 to 20, and specific examples thereof include methoxy group,ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxygroup, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxygroup, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyl oxygroup, decyloxy group, 3,7-dimethyloctyloxy group, lauryl oxy group,trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group,perfluorohexyloxy group, perfluorooctyloxy group, methoxymethyloxygroup, 2-methoxyethyloxy group, etc.

The alkylthio group may be any of linear, branched or cyclic, and mayhave one or more substituents. The number of carbon atoms is usuallyabout 1 to 20, and specific examples thereof include methylthio group,ethylthio group, propylthio group, i-propylthio group, butylthio group,i-butylthio group, t-butylthio group, pentylthio group, hexylthio group,cyclo hexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthiogroup, laurylthio group, trifluoro methylthio group, etc.

The aryl group may have one or more substituents. The number of carbonatoms is usually about 3 to 60, and specific examples thereof includephenyl group and C₁-C₁₂ alkyloxyphenyl group (C₁-C₁₂ shows the number ofcarbon atoms 1-12. hereafter the same), C₁-C₁₂ alkylphenyl group,1-naphtyl group, 2-naphtyl group, pentafluoro phenyl group, etc.

The aryloxy group may have a substituent on the aromatic ring. Thenumber of carbon atoms is usually about 3 to 60, and specific examplesthereof include phenoxy group, C₁-C₁₂ alkyloxy phenoxy group, C₁-C₁₂alkylphenoxy group, 1-naphtyloxy group, 2-naphtyloxy group,pentafluorophenyloxy group, etc.

The arylthio group may have a substituent on the aromatic ring. Thenumber of carbon atoms is usually about 3 to 60, and specific examplesthereof include phenylthio group, C₁-C₁₂ alkyloxyphenylthio group,C₁-C₁₂ alkylphenylthio group, 1-naphthylthio group, 2-naphthylthiogroup, pentafluoro phenylthio group, etc.

The arylalkyl group may have a substituent, and number of carbon atomsis usually about 7 to 60, and specific examples thereof includephenyl-C₁-C₁₂ alkyl group, C₁-C₁₂ alkyloxy phenyl-C₁-C₁₂ alkyl group,C₁-C₁₂ alkylphenyl-C₁-C₁₂ alkyl group, 1-naphtyl-C₁-C₁₂ alkyl group,2-naphtyl-C₁-C₁₂ alkyl group, etc.

The arylalkyloxy group may have a substituent, and number of carbonatoms is usually about 7 to 60, and specific examples thereof includephenyl-C₁-C₁₂ alkyloxy group, C₁-C₁₂ alkyloxy phenyl-C₁-C₁₂ alkyloxygroup, C₁-C₁₂ alkyl phenyl-C₁-C₁₂ alkyloxy group, 1-naphtyl-C₁-C₁₂alkyloxy group, 2-naphtyl-C₁-C₁₂ alkyloxy group, etc.

The arylalkylthio group may have the substituent, and number of carbonatoms is usually about 7 to 60, and specific examples thereof includephenyl-C₁-C₁₂ alkylthio group, C₁-C₁₂ alkyloxyphenyl-C₁-C₁₂ alkylthiogroup, C₁-C₁₂ alkylphenyl-C₁-C₁₂ alkylthio group, 1-naphtyl-C₁-C₁₂alkylthio group, 2-naphtyl-C₁-C₁₂ alkylthio group, etc.

The alkenyl group has usually about 2 to 20 carbon atoms, and specificexamples thereof include vinyl group, 1-propylenyl group, 2-propylenylgroup, 3-propylenyl group, butenyl group, pentenyl group, hexenyl group,heptenyl group, octenyl group, and cyclohexenyl group.

The alkenyl group also include alkadienyl groups, such as 1,3-butadienylgroup.

The alkynyl group has usually about 2 to 20 carbon atoms, and specificexamples thereof include ethynyl group, 1-propynyl group, 2-propynylgroup, butynyl group, pentynyl group, hexynyl group, heptenyl group,octynyl group, and cyclohexyl ethynyl group. The alkynyl group alosinclude alkydienyl groups, such as 1,3-butadiynyl group.

The arylalkenyl group has usually about 8 to 50 carbon atoms The aryland alkenyl in the arylalkenyl group are respectively the same as theabove described aryl group and alkenyl group. Concrete examples thereofinclude 1-arylvinyl group, 2-aryl vinyl group, 1-aryl-1-propylenylgroup, 2-aryl-1-propylenyl group, 2-aryl-2-propylenyl group,3-aryl-2-propylenyl group, etc. Moreover, aryl alkadienyl groups, suchas 4-aryl 1,3-butadienyl group, are also included.

The arylalkynyl group has usually about 8 to 50 carbon atoms. The aryland alkynyl in the arylalkenyl group are respectively the same as theabove described aryl group and alkenyl group. Concrete examples thereofinclude arylethynyl group, 3-aryl-1-propionyl group, 3-aryl-2-propionylgroup, etc. Moreover, arylalkadiynyl groups, such as4-aryl-1,3-butadiynyl, are also included.

As the substituted silyloxy group, silyloxy groups (H₃SiO—) substitutedwith 1, 2, or 3 groups selected from an alkyl group, aryl group,arylalkyl group, and monovalent heterocyclic group, are exemplified. Thealkyl group, aryl group, arylalkyl group, or monovalent heterocyclicgroup may have substituents.

The substituted silyloxy group has usually about 1 to 60 carbon atoms,preferably about 3 to 30 carbon atoms, and specific examples thereofinclude trimethylsilyloxy group, triethylsilyloxy group,tri-n-propylsilyloxy group, tri-1-propylsilyloxy group,t-butylsilyldimethylsilyloxy group, triphenylsilyloxy group,tri-p-xylylsilyloxy group, tribenzylsilyloxy group,diphenylmethylsilyloxy group, t-butyldiphenylsilyloxy group,dimethylphenylsilyloxy group, etc.

As the substituted silylthio group, silylthio groups (H₃SiS—)substituted with 1, 2, or 3 groups selected from an alkyl group, arylgroup, arylalkyl group, and monovalent heterocyclic group, areexemplified. The alkyl group, aryl group, arylalkyl group, or monovalentheterocyclic group may have substituents.

The substituted silylthio group has usually about 1 to 60 carbon atoms,preferably about 3 to 30 carbon atoms, and specific examples thereofinclude trimethylsilylthio group, triethylsilylthio group,tri-n-propylsilylthio group, tri-i-propylsilylthio group,t-butylsilyldimethylsilylthio group, triphenylsilylthio group,tri-p-xylylsilylthio group, tribenzylsilylthio group,diphenylmethylsilylthio group, t-butyldiphenyl silylthio group,dimethylphenylsilylthio group, etc.

As the substituted silylamino group, silylamino groups (H₃SiNH— or(H₃Si)₂N—) substituted with 1 to 6 groups selected from an alkyl group,aryl group, arylalkyl group, and monovalent heterocyclic group, areexemplified. The alkyl group, aryl group, arylalkyl group, or monovalentheterocyclic group may have substituents.

The substituted silylamino group has usually about 1 to 120 carbonatoms, preferably about 3 to 60 carbon atoms, and specific examplesthereof include trimethylsilylamino group, triethylsilylamino group,tri-n-propylsilylamino group, tri-i-propylsilylamino group,t-butylsilyldimethyl silylamino group, triphenylsilylamino group,tri-p-xylyl silylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, t-butyldiphenylsilylamino group,dimethylphenylsilylamino group, di(trimethylsilyl)amino group,di(triethylsilyl)amino group, di(tri-n-propylsilyl)amino group,di(tri-1-propylsilyl)amino group, di(t-butyl silyldimethylsilyl)aminogroup, di(triphenylsilyl)amino group, di(tri-p-xylylsilyl)amino group,di(tribenzylsilyl)amino group, di(diphenylmethylsilyl)amino group,di(t-butyl diphenylsilyl)amino group, di(dimethylphenylsilyl)aminogroup, etc.

As the substituted amino group, amino groups substituted with 1 or 2groups selected from an alkyl group, aryl group, arylalkyl group, andmonovalent heterocyclic group, are exemplified. The alkyl group, arylgroup, arylalkyl group, or monovalent heterocyclic group may havesubstituents.

The substituted amino group has usually about 1 to 40 carbon atoms, andspecific examples thereof include methylamino group, dimethylaminogroup, ethylamino group, diethylamino group, propylamino group,dipropylamino group, isopropylamino group, diisopropylamino group,butylamino group, isobutylamino group, t-butylamino group, pentylaminogroup, hexylamino group, cyclohexylamino group, heptylamino group,octylamino group, 2-ethylhexylamino group, nonylamino group, decylaminogroup, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group,dicyclohexylamino group, pyrrolidyl group, piperidyl group,ditrifluoromethylamino group, phenylamino group, diphenyl amino group,C₁-C₁₂ alkyloxyphenylamino group, di(C₁-C₁₂ alkyloxy phenyl)amino group,di(C₁-C₁₂ alkylphenyl)amino group, 1-naphtylamino group, 2-naphtylaminogroup, pentafluoro phenylamino group, pyridylamino group,pyridazinylamino group, pyrimidylamino group, pyrazylamino group,triazylamino group, phenyl-C₁-C₁₂ alkylamino group, C₁-C₁₂alkyloxyphenyl-C₁-C₁₂ alkylamino group, C₁-C₁₂ alkylphenyl-C₁-C₁₂alkylamino group, di(C₁-C₁₂ alkyloxyphenyl-C₁-C₁₂ alkyl)amino group,di(C₁-C₁₂ alkyl phenyl-C₁-C₁₂ alkyl)amino group, 1-naphtyl-C₁-C₁₂alkylamino group, 2-naphtyl-C₁-C₁₂ alkylamino group, etc.

The amide group has usually about 2 to 20 carbon atoms, and specificexamples thereof include formamide group, acetamide group, propioamidegroup, butyroamide group, benzamide group, trifluoroacetamide group,pentafluoro benzamide group, diformamide group, diacetoamide group,dipropioamide group, dibutyroamide group, dibenzamide group, ditrifluoroacetamide group, dipentafluorobenzamide group, etc.

Examples of the acid imide group include residual groups in which ahydrogen atom connected with nitrogen atom is removed, and have usuallyabout 2 to 60 carbon atoms, preferably 2 to 20 carbon atoms. As theconcrete examples of acid imide group, the following groups areexemplified.

The acyloxy group has usually about 2 to 20 carbon atoms, and specificexamples thereof include acetoxy group, propionyloxy group, butyryloxygroup, isobutyryloxy group, pivaloyloxy group, benzoyloxy group,trifluoroacetyloxy group, pentafluorobenzoyloxy group, etc.

The monovalent heterocyclic group means an atomic group in which ahydrogen atom is removed from a heterocyclic compound. The number ofcarbon atoms is usually about 2 to 60, and specific examples thereofinclude thienyl group, C₁-C₁₂ alkyl thienyl group, pyroryl group, furylgroup, pyridyl group, C₁-C₁₂ alkylpyridyl group, imidazolyl group,pyrazolyl group, triazolyl group, oxazolyl group, thiazole group,thiadiazole group, etc.

The heteroaryloxy group (a group represented by Q⁵-O— and Q⁵ representsa monovalent heterocyclic group) has usually about 2 to 20 carbon atoms,and specific examples thereof include thienyloxy group, C₁-C₁₂alkylthienyloxy group, pyroryloxy group, furyloxy group, pyridyloxygroup, C₁-C₁₂ alkylpyridyloxy group, imidazolyloxy group, pyrazolyloxygroup, triazolyloxy group, oxazolyloxy group, thiazoleoxy group,thiadiazoleoxy group, etc. As Q5, a monovalent aromatic heterocyclicgroup is preferable.

The heteroarylthio group (represented by Q⁶-S—. Q⁶ represents amonovalent heterocyclic group) has usualy about 2 to 60 carbon atoms,and concrete examples thereof include thienyl-mercapto group, C₁-C₁₂alkylthienyl-mercapto group, pyrorylmercapto group, furyl mercaptogroup, pyridylmercapto group, C₁-C₁₂ alkylpyridylmercapto group,imidazolylmercapto group, pyrazolylmercapto group, triazolylmercaptogroup, oxazolylmercapto group, thiazolemercapto group, thiadiazolemercapto group, etc. As Q6, a monovalent aromatic heterocyclic group ispreferable.

In formula (1a), Z¹ represents -M′(=O)_(p)— (wherein, M′ represents anatom of group 3, group 4, group 5, group 6, group 7, group 8, group 9,group 10, group 11, group 12, group 13, group 14, group 15, group 16, orgroup 17, and p represents an integer of 0-2), or represents a b-valentaliphatic hydrocarbon group, b-valent aromatic hydrocarbon group,bidentate heterocyclic group, —C≡N—, —N═N═N—, —NH—, —NH₂—, —OH—, or adirect bond. However, when Z¹ is —C≡N—, —N═N═N—, —NH—, —NH₂—, or —OH—, bis 2. Although —C≡N—, —N═N═N—, —NH₂—, and —OH— are positively charged byitself, the description avout charge is omitted. (Chem. Commun., 1999,1533).

In case Z¹ is -M′(=O)_(p)—, as an atom of group 3, group 4, group 5,group 6, group 7, group 8, group 9, group 10, group 11, group 12, group13, group 14, group 15, group 16, and group 17 in M′, exemplified are aboron atom, carbon atom, nitrogen atom, oxygen atom, fluorine atom,aluminum atom, silicon atom, phosphorus atom, sulfur atom, chlorineatom, scandium atom, titanium atom, vanadium atom, chromium atom,manganese atom, iron atom, cobalt atom, nickel atom, copper atom, zincatom, gallium atom, germanium atom, selenium atom, bromine atom, yttriumatom, zirconium atom, molybdenum atom, palladium atom, hafnium atom,tungsten atom, platinum atom, etc., and preferable is the case where theatomic weight is 50 or less.

In the case where M′ is an atom of group 3 excluding oxygen, group 4,group 5, group 6, group 7, group 8, group 9, group 10, group 11, group12, group 13, group 14, group 15, group 16, and group 17, p can be 1,and when M′ is an atom of group 5, group 6, or group 7, p can be 2.

As the concrete examples where p=1 or 2, —Ti(═O)—, —V(═O)—, —Cr(═O)—,—Cr(═O)₂—, —Zr(═O)—, —Mo(═O)—, —W(═O)—, etc. are exemplified.

The b-valent aliphatic hydrocarbon group in Z¹ represents an atomicgroup in which b pieces of hydrogen atoms are removed from an aliphatichydrocarbon, and may be any of linear, branched or cyclic. It may havesubstituents, and the number of carbon atoms is usually about 1 to 20.Although b is an integer of 2-6, b does not exceed the number ofhydrogens of the aliphatic hydrocarbon group.

Concrete examples of the aliphatic hydrocarbon include methane, ethane,propane, cyclopropane, butane, cyclobutane, 2-methylpropane, pentane,cyclopentane, 2-methylbutane, 2,2-dimethylpropane, hexane, cyclohexane,heptane, octane, 2-ethylhexane, nonane, decane, 3,7-dimethyloctane, etc.

Concrete examples of the divalent aliphatic hydrocarbon group (in caseof b=2) include methylene group, ethylene group, propylene group,trimethylene group, tetramethylene group, pentamethylene group,1,3-cyclopentylene group, 1,4-cyclohexylene group, etc.

In case of b is not less than 3 and not more than 6, concrete examplesthereof following group.

The b-valent aromatic hydrocarbon group in Z¹ represents an atomic groupin which b pieces of hydrogen atoms are removed from an aromatichydrocarbon. It may have substituents on the aromatic ring, and thenumber of carbon atoms is usually about 6 to 60. b does not exceed thenumber of hydrogens of the aromatic ring of the aromatic hydrocarbongroup.

Concrete examples of the aromatic hydrocarbon include benzene and C₁-C₁₂alkyloxybenzene (C₁-C₁₂ shows the number of carbon atoms 1-12. hereafterthe same), C₁-C₁₂ alkylbenzene, naphthalene, anthracene, phenanthrene,tetracene, pentacene, etc.

In case of b=2 (divalent aromatic hydrocarbon group), it represens anatomic group in which two hydrogen atoms are removed from an aromatichydrocarbon group, and the number of carbon atoms is usually about 6 to60, preferably 6 to 20. Examples thereof include phenylene group (forexample, following formulas 1-3), naphthalenediyl group (followingformulas 4-13), anthracenylene group (following formulas 14-19),biphenylene group (following formulas 20-25), triphenylene group(following formulas 26-28), condensed ring compound group (followingformulas 29-38), etc. The number of carbon atoms of substituent R′″ isnot counted as the number of carbon atoms of divalent aromatichydrocarbon group.

R′″ each independently represents a hydrogen atom, halogen atom, alkylgroup, alkyloxy group, alkylthio group, aryl group, aryloxy group,arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthiogroup, alkenyl group, alkynyl group, arylalkenyl group, arylalkynylgroup, substituted silyloxy group, substituted silylthio group,substituted silylamino group, substituted amino group, amide group, acidimide group, acyloxy group, monovalent heterocyclic group, heteroaryloxygroup, heteroarylthio group, acyl group, imine residue, substitutedsilyl group, alkyloxycarbonyl group, aryloxy carbonyl group,arylalkyloxy carbonyl group, heteroaryloxy carbonyl group, carboxylgroup, cyano group, or nitro group.

In case of b is 3 to 6, as the b-valent aromatic hydrocarbon group,exemplified are residues in which (b-2) pieces of R′″s are removed fromthe above examples (1-38) of the divalent aromatic hydrocarbons.

The b-dentate heterocyclic group in Z¹ means a group derived from aheterocyclic compound, and has b pieces of bonding positions. As thebonding positions, a position which bonds to the next atom by thecovalent bond (covalent bond part), and a position which bonds by thecoordinate bond (coordinate-bond part) are exemplified.

As the b-dentate heterocyclic group, exemplified are b-dentate atomicgroups in which at least one hydrogen atom is removed from aheterocyclic compound. They may have substituents, and the number ofcarbon atoms is usually about 2 to 60, and preferably 2 to 20.

As the bidentate heterocyclic group (in case of b=2), exemplified aregroups having two covalent bond part (divalent heterocyclic group) andgroups having one covalent-bond part and one coordinate-bond part(monovalent and bidentate heterocyclic group). As the concrete examplesof the divalent heterocyclic group, following are exemplified.

Divalent heterocyclic groups containing nitrogen as a hetero atom;pyridine-diyl group (following formulas 39-44), diaza phenylene group(following formulas 45-48), quinolinediyl group (following formulas49-63), quinoxalinediyl group (following formulas 64-68), acridinediylgroup (following formulas 69-72), bipyridyldiyl group (followingformulas 73-75), phenanthrolinediyl group (following formulas 76-78),etc.

Groups having a fluorene structure containing silicon, nitrogen, sulfur,selenium, etc. as a hetero atom (following formulas 79-93). It ispreferable to have an aromatic amine monomer containing a nitrogen atom,such as carbazole of formulas 82-84 or triphenylaminediyl group, in viewof light emitting efficiency.

5 membered heterocyclic groups containing silicon, nitrogen, sulfur,selenium, etc. as a hetero atom: (following formulas 94-98).

Condensed 5 membered heterocyclic groups containing silicon, nitrogen,sulfur, selenium, etc. as a hetero atom: (following formulas 99-109),benzothiadiazole-4,7-diyl group, benzo oxadiazole-4,7-diyl group, etc.

5 membered heterocyclic groups containing silicon, nitrogen, sulfur,selenium, etc. as a hetero atom, which are connected at the a positionof the hetero atom to form a dimer or an oligomer (following formulas110-118); and

5 membered ring heterocyclic groups containing silicon, nitrogen,oxygen, sulfur, selenium, as a hetero atom is connected with a phenylgroup at the a position of the hetero atom (following formulas 112-118).

Wherein, R each independently represent a hydrogen atom, halogen atom,alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group,arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthiogroup, alkenyl group, alkynyl group, arylalkenyl group, arylalkynylgroup, substituted silyloxy group, substituted silylthio group,substituted silylamino group, Substituted amino group, amide group, acidimide group, acyloxy group, monovalent heterocyclic group, heteroaryloxygroup, heteroarylthio group, acyl group, imine residue, substitutedsilyl group, alkyloxy carbonyl group, aryloxycarbonyl group,arylalkyloxy carbonyl group, heteroaryloxycarbonyl group, carboxylgroup, cyano group, or nitro group.

Concrete examples of the monovalent and bidentate heterocyclic groupinclude: groups derived from the divalent heterocyclic group of theabove 39-118 in which one of the connecting bonds is replaced by R, andfurther has a coordinate bond on the hetero atom; and the followinggroups.

When b is 3-6, as the b-valent heterocyclic group (having b peices ofcovalent-bond parts), the residue in which (b-2) pieces of hydrogenatoms are removed from the above examples of divalent heterocyclicgroup.

V¹ in formula (1a) represents a group 16 atom, divalent aliphatichydrocarbon group, divalent aromatic hydrocarbon group, bidentateheterocyclic group, —C≡N—, —N═N═N—, or a direct bond, and a plurality ofV¹ may be the same or different, respectively. Z¹ and V¹ are not thesame.

Examples of the group 16 atom in V¹ include an oxygen atom, sulfur atom,selenium atom, and tellurium atom, and preferably an oxygen atom andsulfur atom.

The definition and concrete examples of the divalent aliphatichydrocarbon group in V¹ are the same as those in the above Z¹.

The definition and concrete examples of the divalent aromatichydrocarbon group in V¹ are the same as those of the above Z¹.

The definition and concrete examples of the bidentate heterocyclic groupin V¹ are the same as those of the above Z¹.

In formula (1a), a represents an integer of not less than 1 and not morethan 3, preferably an integer of 2 or 3, and more preferably 3.

In formula (1b), k represents an integer of not less than 1 and not morethan 4, preferably an integer of not less than 3 in view of making along-life device, and more preferably k=4.

In formula (1a), b represents an integer of not less than 2 and not morethan 6. However, when V¹ is —C≡N—, —N═N═N— or a direct bond, b is 2.

In formula (1a), c represents an integer of not less than 1 and not morethan 6.

Concrete examples of the negative ion represented by the above formula(1a) include negative ions represented by VI or VII described below.

Among the negative ions represented by the above formula (1a), in viewof long-life, the case where Ar¹ is a perfluoroaryl group is preferable,and the case where a is 2 or 3, is further preferable.

The case where Z¹ or V¹ is —C≡N—, is more preferable. Concretely, thenegative ions represented by the above formula VII are exemplified.

More preferable is the case where the above formula (1a) is the belowformula (5-1) or (5-2).[(C₆F₅)₃B—C≡N—B(C₆F₅)₃]⁻  (5-1)[M{C≡N—B(C₆F₅)₃}₄]²⁻  (5-2)(wherein, M represents a nickel atom or a palladium atom.)

Among the negative ions represented by the above formula (1b), in viewof long-life, the case where Ar¹ is a perfluoroaryl group is preferable,and the case where k is 3 or 4, is more preferable.

Among the negative ions represented by formula (1b), the case Y is aboron atom is preferable, and the case where it is represented by (1-1)is more preferable in view of long-life.

(wherein, Ar¹, X, and k represent the same meaning as the above.)

More preferable is the case where the above formula (1b-1) isrepresented by the below formula (1b-2).[B(Ar^(1b))₄]⁻  (1b-2)(wherein, Ar^(1b) represents a phenyl group substituted by two or moregroup selected from fluorine and trifluoromethyl group. Ar^(1b)s may bethe same or diferent.

In formula (1b-2), the case where all Ar^(1b)s are the same ispreferable.

As the examples, exemplifed are those represented by the below formulas(12) and (13), and those represented by formula (12) is preferable.

The case where the above formula (1b-1) is represented by the belowformula (1b-3) is also preferable.

Wherein, X represents the same meaning as the above. Ar^(1c) representsa perfluoroaryl group and f represents an integer of 3 or 4.

Concretely, the following negative ions are exemplified.

As for the ion pair used for the composition of the present invention,the negative ions are represented by the above formula (1a), (1b), (2)or (3).

Among them, the negative ion of formula (2) represents

(wherein, Y² represents a group 13 atom and Ar² represents an aryl grouphaving an electron-withdrawing group, or a monovalent heterocyclic grouphaving an electron-withdrawing group. Q² represents an oxygen atom or adirect bond. X² represents a halogen atom, alkyl group, alkyloxy group,alkylthio group, aryl group, aryloxy group, arylthio group, arylalkylgroup, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynylgroup, arylalkenyl group, arylalkynyl group, substituted silyloxy group,substituted silylthio group, substituted silylamino group, substitutedamino group, amide group, acid imide group, acyloxy group, monovalentheterocyclic group, heteroaryloxy group, heteroarylthio group, cyanogroup, or nitro group. d and d′ each independently represents 1 or 2. V²represents a group 16 atom, divalent aliphatic hydrocarbon group,divalent aromatic hydrocarbon group, bidentate heterocyclic group, —C≡N—or —N═N—. A plurality of Y², Ar², Q² and V² may be the same ordifferent, and when two or more X² exist, they may be the same ordifferent. e represents an integer of 1-6.).

Concrete examples of group 13 atom in Y² is the same as those of theabove Y¹. The definition and the concrete examples of the aryl grouphaving electron-withdrawing group and the monovalent heterocyclic grouphaving electron-withdrawing group in Ar² are the same as those of theabove Ar¹.

In X², the definition and the concrete examples of halogen atom, alkylgroup, alkyloxy group, alkylthio group, aryl group, aryloxy group,arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthiogroup, alkenyl group, alkynyl group, arylalkenyl group, arylalkynylgroup, substituted silyloxy group, substituted silylthio group,substituted silylamino group, substituted amino group, amide group, acidimide group, acyloxy group, monovalent heterocyclic group, heteroaryloxygroup, and heteroarylthio group, are the same as those of the above X².In V², the definition and the concrete examples of group 16 atom,divalent aliphatic hydrocarbon group, divalent aromatic hydrocarbongroup, and bidentate heterocyclic group, are the same as those in theabove V¹.

As the negative ion represented by the above formula (2), concretelyexemplified are the negative ions represented by below formula VIII.

Among the negative ions represented by the above formula (2), the casewhere Ar² is perfluoro aryl group is preferable in view of long-life,and the case where Ar² is a perfluoro aryl group and d and d′ are 2, ismore preferable.

As for the ion pair used for the composition of the present invention,the negative ion is represented by the above formula (1a), (1b), (2), or(3), and among the negative ion of formula (3) represent,

(wherein, Y³ represents a group 13 atom and Ar³ represents an aryl grouphaving an electron-withdrawing group, or a monovalent heterocyclic grouphaving an electron-withdrawing group. Q³ represents an oxygen atom or adirect bond. V³ represent a group 16 atom, divalent aliphatichydrocarbon group, divalent aromatic hydrocarbon group, bidentateheterocyclic group, —C≡N—, or —N═N—. A plurality of Y³, Ar³, Q³ and V³are respectively the same or different. f represents an integer of1-6.).

Concrete examples of group 13 atom in Y³ is the same as those of theabove Y¹, and the definition and the concrete examples of the aryl grouphaving the electron-withdrawing group and the monovalent heterocyclicgroup having an electron-withdrawing group in Ar³ are the same as thoseof the above Ar¹. In V³, the definition and the concrete examples ofgroup 16 atom, divalent aliphatic hydrocarbon group, divalent aromatichydrocarbon group, and bidentate heterocyclic group, are the same asthose of V¹.

As the negative ion represented by the above formula (3), concretelyexemplified are the negative ions represented by below formula IX.

In the above formula VI-IX, substituents may be contained on thearomatic hydrocarbon ring, heterocycle, or hydrocarbon chain.

Among the negative ions represented by the above formula (3), the casewhere Ar is a perfluoroaryl group is preferable in view of long-life.

Among the negative ions represented by the above formula (1a), (1b),(2), and (3), an ion pair which contains the negative ion represented by(1a) is preferable.

Next, the positive ion of the ion pair contained in the composition ofthe present invention is described. As the positive ion, exemplifiedare: carbocation; onium of the element selected from a nitrogen atom, anoxygen atom, a phosphorus atom, a sulfur atom, a chlorine atom, aselenium atom, a bromine atom, a tellurium atom, and an iodine atom; ahydrogen ion, and a metal cation.

The carbocation may be monovalent, or polyvalent such as di-valent ormore, and examples thereof include methylium, ethylium, neopentylinium,cyclopropenylium, phenylium, anthrylium, and triphenylmethylium.

The onium of nitrogen atom may be monovalent, or polyvalent such asdi-valent or more, and examples thereof include monovalent aliphaticammonium salts shown by below formulas.

Cyclic aliphatic ammonium salts represented by the below formula,

Aromatic ammonium salts represented by the below formula,

Onium of heterocycles containing nitrogen atom represented by the belowformula,

The below formula (6)

Wherein, R³ and R⁴ each independently represent alkyl group, alkyloxygroup, aryl group, aryloxy group, arylalkyl group, arylalkyloxy group,acyl group, acyloxy group, monovalent heterocyclic group, orheteroaryloxy group. R⁵ and R⁶ each independently represent a halogenatom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxygroup, arylthio group, arylalkyl group, arylalkyloxy group,arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group,arylalkynyl group, substituted silyloxy group, substituted silylthiogroup, substituted silylamino group, substituted amino group, amidegroup, acid imide group, acyloxy group, monovalent heterocyclic group,heteroaryloxy group, hetero arylthio group, acyl group, imine residue,substituted silyl group, alkyloxycarbonyl group, aryloxycarbonyl group,arylalkyloxycarbonyl group, heteroaryloxycarbonyl group, carboxyl group,cyano group, or nitro group. T represents a direct bond, divalentaliphatic hydrocarbon group, divalent aromatic hydrocarbon group,alkenylene group, ethynylene group, or a divalent heterocyclic group. iand j each independently represent an integer of 0-4. When two or moreR⁵ and R⁶ exist, respectively, they may be the same or different.

In R³, R⁴, R⁵, and R⁶, the definition and the concrete examples ofhalogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group,aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group,arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group,arylalkynyl group, substituted silyloxy group, substituted silylthiogroup, substituted silylamino group, substituted amino group, amidegroup, acid imide group, acyloxy group, monovalent heterocyclic group,heteroaryloxy group, and heteroarylthio group are the same as those ofthe above X¹ and X². The definition and the concrete examples of acylgroup, alkyloxycarbonyl group, aryloxycarbonyl group,alkylalkyloxycarbonyl group, and heteroaryloxy carbonyl group are thesame as those of the electron-withdrawing groups in the above Ar¹, Ar²,and Ar³.

Imine residue is a residue in which a hydrogen atom is removed from animine compound (an organic compound having —N═C— is in the molecule.Examples thereof include aldimine, ketimine, and compounds whosehydrogen atom on N is substituted with an alkyl group etc.), and usuallyhas about 2 to 60 carbon atoms, preferably 2 to 20 carbon atoms. As theconcrete examples, groups represented by below structural formulas areexemplified.

The substituted silyl group represents a silyl group substituted by 1,2, or 3 groups selected from an alkyl group, aryl group, arylalkylgroup, and monovalent heterocyclic group. The number of carbon atoms isusually about 1 to 60, and preferably 3-30. The alkyl group, aryl group,arylalkyl group, or monovalent heterocyclic group may have substituents.Examples thereof include trimethylsilyl group, triethylsilyl group,tri-n-propylsilyl group, tri-i-propylsilyl group,t-butylsilyldimethylsilyl group, triphenylsilyl group, tri-p-xylylsilylgroup, tribenzylsilyl group, diphenylmethyl silyl group,t-butyldiphenylsilyl group, dimethylphenylsilyl group, etc.

The definition and the concrete examples of the divalent aliphatichydrocarbon group and divalent aromatic hydrocarbon group in T of theabove formula (6) are the same as those of the above V¹, V², and V³.

The divalent heterocyclic group means an atomic group in which twohydrogen atoms are removed from a heterocyclic compound, and the numberof carbon atoms is usually about 2 to 60, and preferably 2 to 20.Substituent may be contained on the divalent heterocyclic group, and thenumber of carbon atoms of the substituent is not counted as the numberof carbon atoms of divalent heterocycle.

As the concrete examples of the divalent heterocyclic group, the groupsexemplified for the above Z¹ are exemplified.

The alkenylene group has usually about 20 to 20 carbon atoms, andexamples thereof include vinylene group, propylene group, etc. Thealkenylene group include alkadienylene groups, such as 1,3-butadienylenegroup.

The alkynylene group usually has about 2 to 20 carbon atoms, andexemples thereof include ethynylene group etc. The alkynylene group alsoincludes a group having two triple bonds, for example,1,3-butanediynylene group.

As the concrete example of formula (6), the following is exemplified.

The case where the positive ion of the ion pair is a divalent positiveion represented by the above formula (6), is preferable in view ofluminescence strength.

The onium of oxygen atom may be monovalent, or polyvalent such asdi-valent or more, and examples thereof include trimethyl oxonium,triethyl oxonium, tripropyl oxonium, tributyl oxonium, trihexyl oxonium,triphenyl oxonium, pyrrylinium, chromenylium, and xanthylium.

The onium of phosphorus atom may be monovalent, or polyvalent such asdi-valent or more, and examples thereof include tetramethyl phosphonium,tetraethyl phosphonium, tetrapropyl phosphonium, tetrabutyl phosphonium,tetrahexyl phosphonium, tetraphenyl phosphonium, triphenylmethylphosphonium, and methyltriphenyl phosphonium.

The onium of sulfur atom may be monovalent, or polyvalent such asdi-valent or more, and examples thereof include aliphatic sulfoniums,such as trimethyl sulfonium, triethyl sulfonium, tripropyl sulfonium,tributyl sulfonium, and trihexyl sulfonium; aromatic sulfoniums, such astriphenyl sulfonium, tri(4-methylphenyl)sulfonium, and tri(4-t-butylphenyl)sulfonium, methyldiphenyl sulfonium, dimethylphenyl sulfonium,and oniums of the following formulas.

The onium of chlorine atom may be monovalent, or polyvalent such asdi-valent or more, and examples thereof include dimethyl chloronium,diethyl chloronium, dipropyl chloronium, dibutyl chloronium, diphenylchloronium, and methylphenyl chloronium.

The onium of selenium atom may be monovalent, or polyvalent such asdi-valent or more, and examples thereof include trimethyl selenium,triethyl selenium, tripropyl selenium, tributyl selenium, trihexylselenium, triphenyl selenium, tri(4-methylphenyl)selenium, tri(4-t-butylphenyl)selenium, methyldiphenyl selenium, and dimethylphenyl selenium.

The onium of bromine atom atom may be monovalent, or polyvalent such asdi-valent or more, and examples thereof include dimethyl bromonium,diethyl bromonium, dipropyl bromonium, dibutyl bromonium, diphenylbromonium, and methylphenyl bromonium.

The onium of tellurium atom may be monovalent, or polyvalent such asdi-valent or more, and examples thereof include trimethyl telluronium,triethyl telluronium, tripropyl telluronium, tributyl telluronium,trihexyl telluronium, triphenyl telluronium,tri(4-methylphenyl)telluronium, tri(4-t-butylphenyl)telluronium,methyldiphenyl telluronium, and dimethylphenyl telluronium.

The onium of iodine atom may be monovalent, or polyvalent such asdi-valent or more, and examples thereof include dimethyl iodonium,diethyl iodonium, dipropyl iodonium, dibutyl iodonium, diphenyliodonium, di(t-butylphenyl)iodonium,4-methylphenyl-4-(1-methylethyl)phenyl iodonium, methylphenyl iodonium,or oniums of the below formulas.

Examples of the metal cation include a cation of alkali metal, a cationof alkaline-earth metal, a cation of rare-earth element, a cation of atransition metal, etc., and they may be monovalent, or polyvalent suchas di-valent or more.

Since optical quenching by heavy atom effect may occur, it is preferablethat the atomic weight is less than 50.

Concrete examples of the cation of alkali metal include lithium ion,sodium ion, potassium ion, rubidium ion, cesium ion, and francium ion.

Concrete examples of the cation of alkaline earth metal includeberyllium ion, magnesium ion, calcium ion, strontium ion, barium ion,(MgCl)⁺, and (MgBr)⁺ and (MgI)⁺.

Concrete examples of the cation of rare-earth elements include scandiumion and yttrium ion. Concrete examples of the cation of the transitionmetal include titanium ion, zirconium ion, hafnium ion, vanadium ion,chromium ion, [bis(η⁵-benzene)Cr]⁺, manganese ion, iron ion,[(η⁵-cyclopentadienyl)(η⁶-benzene)Fe]⁺,[(η⁵-cyclopentadienyl)(η⁶-toluene)Fe]⁺ and[(η⁵-cyclopentadienyl)(η⁶-1-methyl naphthalene)Fe]⁺,[(η⁵-cyclopentadienyl)(η⁶-cumene)Fe]⁺, [bis(η⁵-mesitylene)Fe]⁺, cobaltion, nickel ion, copper ion, zinc ion, etc.

As the ion pair used for the present invention, following compounds arespecifically exemplified.

As those whose positive ion is carbocation, following ion pairs areexemplified.

As those whose positive ion is onium of nitrogen atom, exemplifeid arethose of aromatic ammonium salts, those of aliphatic ammonium salts,those of aromatic aminium salts, and those of aromatic diazonium salts.Examples of those of aromatic ammonium salts include1-benzyl-2-cyanopyridinium tetrakis(pentafluorophenyl)borate, 1-(naphtylmethyl)-2-cyanopyridinium tetrakis(pentafluorophenyl)borate,N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,1-butyl-3-methylimidazolium tetrakis(pentafluorophenyl)borate,1-ethyl-3-methylimidazolium tetrakis(pentafluorophenyl)borate,1-octyl-3-methylimidazolium tetrakis(pentafluoro phenyl)borate,tris(4-bromophenyl)aminium tetrakis(pentafluorophenyl)borate.

Examples of those of aliphatic ammonium salts includetetrabutylammonium, tetrakis(pentafluorophenyl)borate,tetraethylammonium tetrakis(pentafluorophenyl)borate.

Examples of those of aromatic aminium salts includetris(4-bromophenyl)aminium, tetrakis(pentafluorophenyl)borate,N,N,N′,N′-tetraphenyl-4,4′-biphenylene diaminiumbis(tetrakis(pentafluorophenyl)borate).

Examples of those of aromatic diazonium salts include phenyldiazoniumtetrakis(pentafluorophenyl)borate.

Examples of those of aromatic ammonium salts include new compoundsrepresented by the below formula (10).

wherein, R³, R⁴, R⁵, R⁶, and T represent the same meaning as the above.

Compounds represented by the above formula (10), the following compoundsare exemplified.

Compounds represented by formula (10) can be produced, for example, byreacting a compound represented by the below formula (11), withLi[B(C₆F₅)₄].n(Et₂O).

[wherein R³, R⁴, R⁵, R⁶ and T represent the same meaning as above. X¹⁻and X²⁻ each independently represent a halide ion, alkylsulfonate ion,and arylsulfonate ion.]

As the halide ion, fluoride ion, chloride ion, bromide ion, and iodideion are exemplified.

As the alkylsulfonate ion, methanesulfonate ion, ethane sulfonate ion,and trifluoromethanesulfonate ion are exemplified.

As the arylsulfonate ion, benzenesulfonate ion and p-toluenesulfonateion are exemplified.

As those of the aromatic ammonium salts, the following ion pairs areadditionally exemplified.

As those of the aliphatic ammonium salts, the following ion pairs areadditionally exemplified.

As those of the aromatic aminium salts, the following ion pairs areadditionally exemplified.

As those of the aromatic diazonium salts, the following ion pairs areadditionally exemplified.

As those whose positive ion is onium of phosphorus atom,tetraphenylphosphonium tetrakis(pentafluorophenyl)borate is exemplified.As those whose positive ion is onium of phosphorus atom, the followingion pairs are additionally exemplified.

As those whose positive ion is onium of sulfur atom, those of aromaticsulfonium salts are exemplified. Examples thereof includebis[4-(diphenylsulfonio)phenyl]sulfide tetrakis(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenyl sulfoniumtetrakis(pentafluorophenyl)borate, triphenyl sulfoniumtetrakis(pentafluorophenyl)borate,bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide tetrakis(pentafluorophenyl)borate. As those whose positive ion is onium ofsulfur atom, the following ion pairs are additionally exemplified.

As those whose positive ion is onium of iodine atom, those of aromaticiodonium salts are exemplified. Examples thereof include diphenyliodonium tetrakis(pentafluorophenyl)borate, bis(dodecyl phenyl)iodoniumtetrakis(pentafluorophenyl)borate,4-methylphenyl-4-(1-methylethyl)phenyl iodoniumtetrakis(pentafluorophenyl)borate [“Rhodrsil photoinitiator PI-2074”light polymerization initiator, commercially available by Rhodia]. Asthose whose positive ion is onium of iodine atom, the following ionpairs are additionally exemplified.

As those whose positive ion is a metal cation, examples thereof include(2,4-cyclopentadiene-1-yl)[(1-methyl ethyl)benzene]-Fe(II)tetrakis(pentafluorophenyl)borate. As those whose positive ion is ametal cation, the following ion pairs are additionally exemplified.

The present invention provides a new ion pair wherein the negative ionis represented by the following structural formula (5-1), and thepositive ion is a pyridinium cation, a phosphonium cation, or a iodoniumcation.[(C₆F₅)₃B—C≡N—B(C₆F₅)₃]⁻  (5-1)

Concrete examples are shown below.

As the ion pair whose positive ion is a pyridinium cation, the followingcompounds are exemplified.

As the ion pair whose positive ion is a phosphonium cation, thefollowing compounds are exemplified.

As the ion pair whose positive ion is a iodonium cation, the followingcompounds are exemplified.

The above pyridinium salt, phosphonium salt, and iodonium salt can beproduced, for example, by reacting a compound represented by the belowformula (7-1), with K[(C₆F₅)₃B—C≡N—B(C₆F₅)₃] represented by the belowformula (7-1).E¹⁺X¹⁻  (7-1)wherein, E¹⁺ represents a pyridinium cation, a phosphonium cation, or aiodonium cation. X¹⁻ represents a halide ion, alkylsulfonate ion, andarylsulfonate ion.

As the halide ion, fluoride ion, chloride ion, bromide ion, and iodationthing ion are exemplified.

As the alkylsulfonate ion, methanesulfonate ion, ethane sulfonate ion,and trifluoromethanesulfonate ion are exemplified.

As the arylsulfonate ion, benzene sulfonate ion and p-toluene sulfonateion are exemplified.

The present invention provides a new ion pair wherein the negative ionis represented by the following structural formula (5-2), and thepositive ion is a pyridinium cation, a quarternary ammonium cation, aphosphonium cation, an oxonium cation, a sulfonium cation, or a iodoniumcation.[M{C≡N—B(C₆F₅)₃}₄]²⁻  (5-22)(wherein, M represents a nickel atom or a palladium atom.)

Concrete examples are shown below.

As the ion pair whose positive ion is a pyridinium cation, the followingcompounds are exemplified.

As the ion pair whose positive ion is a quarternary ammonium cation, thefollowing compounds are exemplified.

As the ion pair whose positive ion is a phosphonium cation, thefollowing compounds are exemplified.

As the ion pair whose positive ion is a oxonium cation, the followingcompounds are exemplified.

As the ion pair whose positive ion is a sulfonium cation, the followingcompounds are exemplified.

As the ion pair whose positive ion is a iodonium cation, the followingcompounds are exemplified.

The above pyridinium salt, phosphonium salt, and iodonium salt can beproduced, for example, by reacting a compound represented by the belowformula (7-2), with K₂[M{C≡N—B(C₆F₅)₃}₄]E²⁺X²⁻  (7-2)wherein, E²⁺ represents a pyridinium cation, a quarternary ammoniumcation, a phosphonium cation, an oxonium cation, a sulfonium cation, ora iodonium cation. X²⁻ represents a halide ion, alkylsulfonate ion, andarylsulfonate ion.

As the concrete examples of the halide ion, alkylsulfonate ion, andarylsulfonate ion, the ions for the above X¹⁻ can be exemplified.

In the present invention, the ion pair added to the light-emittingpolymer composition may be any of one kind or 2 kinds or more.

Next, the light-emitting polymer used for the present invention isexplained.

The polystyrene reduced number average molecular weight of thelight-emitting polymer used for the present invention is usually10³-10⁸. Among the light-emitting polymer of the present invention, aconjugated polymer compound is preferable. The conjugated polymercompound means a polymer compound where delocalized π electron pairexists along with the main-chain of the polymer compound. As thedelocalized electron, an unpaired electron or an isolated electron pairmay participate in the resonance instead of a double bond.

The light-emitting polymer used for the present invention may be ahomopolymer of a copolymer, and examples thereof include: polyfluorene[for example, Jpn. J. Appl. Phys., volume 30, L1941 (1991)];poly-paraphenylene [for example, Adv. Mater., volume 4, page 36 (1992)];polyarylenes such as polypyrrol, polypyridine, polyaniline,polythiophene, etc.; polyarylenevinylenes, such as polypara-phenylenevinylene and poly thienylenevinylene (for example, WO98/27136); polyphenylene sulfide, polycarbazole, etc.

[for example, “Advanced Materials vol. 12 1737-1750 (2000) and “OrganicEL Display Technology, Monthly Display, December issue, P. 68-73”]

Among them, the light-emitting polymer of polyarylene type ispreferable.

As the repeating unit contained in the light-emitting polymer ofpolyarylenes, an arylene group and a divalent heterocyclic group areexemplified, and those consisting of these repeating units 20-100% bymole is preferable, and those consisting of 50-99% by mole is morepreferable.

The number of carbon atoms constituting the ring of the arylene group isusually about 6 to 60. Concrete examples thereof include phenylenegroup, biphenylene group, terphenylene group, naphthalenediyl group,anthracenediyl group, phenanthrenediyl group, pentalene-diyl group,indene diyl group, heptalenediyl group, indacenediyl group,triphenylenediyl group, binaphthyldiyl group, phenyl naphthylenediylgroup, stilbenediyl group, fluorenediyl group (for example, the casewhere A=—C(R′)(R′)— in the below formula (4)).

The number of carbon atoms constituting the ring of the divalentheterocyclic group is usually about 3 to 60. Concrete examples thereofinclude pyridinediyl group, diazaphenylene group, quinolinediyl group,quinoxalinediyl group, acridine diyl group, bipyridyldiyl group,phenanthrolinediyl group, and in the below formula (4), the case wherethey are X=—O—, —S—, —Se—, —NR″—, —C(R′)(R′)—, or —Si(R′)(R′)—.

Furthermore, the case where the repeating unit shown by a below formula(4) is contained, is preferable.

(wherein, A represents an atom or an atomic group for forming the 5membered ring or 6 membered ring together with 4 carbon atoms on twobenzene rings of the formula; R^(4a), R^(4b), R^(4c), R^(5a), R^(5b),and R^(5c) each independently represent a hydrogen atom, a halogen atom,alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group,arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthiogroup, alkenyl group, alkynyl group, arylalkenyl group, arylalkynylgroup, acyl group, acyloxy group, amide group, acidimide group, imineresidue, substituted amino group, substituted silyl group, substitutedsilyloxy group, substituted silylthio group, substituted silylaminogroup, cyano group, nitro group, monovalent heterocyclic group,heteroaryloxy group, hetero arylthio group, alkyloxy carbonyl group,aryloxy carbonyl group, arylalkyloxy carbonyl group, heteroaryloxycarbonyl group, or carboxyl group; R^(4b) and R^(4c), and R^(4b) andR^(5c) may respectively form a ring, together.).

A represents an atom or an atomic group for forming the 5 membered ringor 6 membered ring together with 4 carbon atoms on two benzene rings ofthe formula, and concrete examples thereof include the followingswithout being limited.

wherein, R and R′ and R″ each independently represent a halogen atom,alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group,arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthiogroup, alkenyl group, alkynyl group, arylalkenyl group, arylalkynylgroup, acyloxy group, substituted amino group, substituted silyloxygroup, substituted silylthio group, substituted silylamino group, cyanogroup, or monovalent heterocyclic group. R′ each independentlyrepresents a hydrogen atom, halogen atom, alkyl group, alkyloxy group,alkylthio group, aryl group, aryloxy group, arylthio group, arylalkylgroup, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynylgroup, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group,amide group, acid imide group, imine residue, substituted amino group,substituted silyl group, substituted silyloxy group, substitutedsilylthio group, substituted silylamino group, cyano group, nitro group,or monovalent heterocyclic group. R″ each independently represents ahydrogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group,aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group,arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group,arylalkynyl group, acyl group, substituted silyl group, substitutedsilyloxy group, substituted silylthio group, substituted silylaminogroup, or monovalent heterocyclic group.

As the halogen atom, alkyl group, the alkyloxy group, alkylthio group,aryl group, aryloxy group, arylthio group, Arylalkyl group, thearylalkyloxy group, the arylalkylthio group, Alkenyl group, alkynylgroup, the arylalkenyl group, the arylalkynyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group,substituted amino group, amide group, acid imide group, acyl group, theacyloxy group, and a monovalent heterocyclic group in R, R′, and R″, thedefinition and the concrete examples are the same as those of the aboveR³, R⁴, R⁵, and R⁶.

Among A, —O—, —S—, —Se—, —NR″—, —CR′R′— and —SiR′R′— are preferable, and—O—, —S—, and —CR′R′— are more preferable.

The halogen atom, alkyl group, alkyloxy group, alkylthio group, arylgroup, aryloxy group, arylthio group, arylalkyl group, arylalkyloxygroup, arylalkylthio group, alkenyl group, alkynyl group, arylalkenylgroup, arylalkynyl group, acyl group, acyloxy group, amide group, acidimide group, imine residue, substituted amino group, substituted silylgroup, substituted silyloxy group, substituted silylthio group,substituted silylamino group, cyano group, nitro group, monovalentheterocyclic group, heteroaryloxy group, hetero arylthio group,alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxy carbonylgroup, and heteroaryloxy carbonyl group in R^(4a), R^(4b), R^(4c),R^(5a), R^(5b), R^(5c), are the same as those of the above.

As the repeating unit represented by the above formula (4), thefollowing structures are exemplified.

wherein, the hydrogen atom on benzene ring may be replaced with ahalogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group,aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group,arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group,arylalkynyl group, acyl group, acyloxy group, amide group, acid imidegroup, imine residue, substituted amino group, substituted silyl group,substituted silyloxy group, substituted silylthio group, substitutedsilylamino group, cyano group, nitro group, or monovalent heterocyclicgroup. When two substituents exist in the adjacent position of thebenzene ring, they may be connected to form a ring.

The light-emitting polymer used for the present invention may comprise arepeating unit, for example, derived from an aromatic amine, besides thearylene group and the divalent heterocyclic group. In this case, a holeinjection property and transportation property can be afforded.

In this case, the molar ratio of the repeting group consisting of anarylene group and a divalent heterocyclic group to the repeating unitderived from an aromatic amine is usually 99:1-20:80.

As the repeating unit derived from aromatic amine, the repeating unitsrepresented by the below formula (8) are preferable.

wherein, Ar⁴, Ar⁵, Ar⁶, and Ar⁷ each independently represent an arylenegroup or a divalent heterocyclic group. Ar⁸, Ar⁹, and Ar¹⁰ eachindependently represent an aryl group or a monovalent heterocyclicgroup. o and p each independently represent 0 or 1, and 0<=o+p<=2.

Here, the definition and the concrete examples of the arylene group anddivalent heterocyclic group are the same as those of the above T. Thedefinition and the concrete examples of the aryl group and monovalentheterocyclic group are the same as those of the above X¹ and X².

As a concrete example of the repeating unit represented by the aboveformula (8), the following structures are exemplified.

wherein, the hydrogen atom on the aromatic ring may be replaced by ahalogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group,aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group,arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group,arylalkynyl group, acyl group, acyloxy group, amide group, acid imidegroup, imine residue, substituted amino group, substituted silyl group,substituted silyloxy group, substituted silylthio group, substitutedsilylamino group, cyano group, nitro group, monovalent heterocyclicgroup, heteroaryloxy group, hetero arylthio group, alkyloxy carbonylgroup, aryloxy carbonyl group, arylalkyloxycarbonyl group,heteroaryloxycarbonyl group, and carboxyl group.

Among the repeating unit represented by the above formula (8), therepeating units represented by the below formula (9) are especiallypreferable.

wherein, R7, R8, and R9 each independently represent a halogen atom,alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group,arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthiogroup, alkenyl group, alkynyl group, arylalkenyl group, The arylalkynylgroup, acyl group, the acyloxy group, amide group, acid imide group,imine residue, substituted amino group, substituted silyl group,substituted silyloxy group, substituted silylthio group, substitutedsilylamino group, cyano group, nitro group, monovalent heterocyclicgroup, heteroaryloxy group, heteroarylthio group, alkyloxycarbonylgroup, aryloxycarbonyl group, arylalkyloxy carbonyl group, heteroaryloxycarbonyl group, or carboxyl group. x and y each independently representan integer of 0-4. z represents an integer of 0-2. w represents aninteger of 0-5.

The light-emitting polymer used for the present invention may also be arandom, block or graft copolymer, or a polymer having an intermediatestructure thereof, for example, a random copolymer having blockproperty. From the viewpoint for obtaining a polymer compound havinghigh fluorescent quantum yield, random copolymers having block propertyand block or graft copolymers are preferable than complete randomcopolymers. Further, a polymer having a branched main chain and morethan three terminals, and a dendrimer may also be included.

As for the end groups of the light-emitting polymer used for the presentinvention, if the polymerizable group remains intact, there is apossibility of reduction in light emitting property and life-time whenmade into an device, and they may be protected with a stable group.Those having a conjugated bond continuing to a conjugated structure ofthe main chain are preferable, and there are exemplified structuresconnected to an aryl group or heterocyclic compound group via acarbon-carbon bond. Specifically, substituents described as ChemicalFormula 10 in JP-A-9-45478 are exemplified.

The light-emitting polymer used for the present invention, it ispreferable that the polystyrene reduced number average molecular weightsis about 10³-10⁸, and preferably the polystyrene reduced number averagemolecular weights is about 10⁴-10⁶.

Moreover, since light emission from a thin film is used, as thelight-emitting polymer, those having light-emission in the solid stateis used preferably.

Methods of synthesizing the light-emitting polymer used for the presentinvention include, for example: a method of polymerization ofcorresponding monomers by Suzuki coupling reaction; a method ofpolymerization by Grignard reaction; a method of polymerization by Ni(0)catalyst; a method of polymerization using an oxidizer, such as, FeCl₃,etc.; a method of electrochemical oxidization polymerization; and amethod by decomposition of an intermediate polymer having a suitableleaving group. Among these, a method of polymerization by Suzukicoupling reaction; a method of polymerization by Grignard reaction; amethod of polymerization by Ni(0) catalyst are preferable, because thereaction is easily controllable.

When the light-emitting polymer is used as a light emitting material ofa polymer LED, the purity thereof exerts an influence on light emittingproperty, therefore, it is preferable that a monomer beforepolymerization is purified by a method such as distillation, sublimationpurification, re-crystallization and the like before being polymerizedand further, it is preferable to conduct a purification treatment suchas re-precipitation purification, chromatographic separation and thelike after the synthesis.

The light-emitting polymer composition of the present inventioncomprises a light-emitting polymer and an ion pair. The content of theion pair is usually 0.001-10 parts by weight based on 100 parts byweight of the light-emitting polymer, preferably 0.001-5 parts byweight, more preferably 0.001-1 parts by weight, and further preferably0.01-1 parts by weight.

Furthermore, the light-emitting polymer solution composition of thepresent invention comprises a light-emitting polymer, and an ion pairand a solvent.

Using this solution composition, a light emitting layer can be formed bycoating method. The light emitting layer produced by using this solutioncomposition usually contains the light-emitting polymer composition ofthe present invention.

As the solvent, chloroform, methylene chloride, dichloro ethane,tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin,n-butylbenzene, etc., are exemplified.

The light-emitting polymer, although being depend the structure and themolecular weight thereof, can usually dissolve 0.1% by weight or more inthese solvents.

The amount of the solvent is usually about 1000-100000 parts by weightbased on 100 parts by weight of the light-emitting polymer.

The composition of the present invention may contain a coloring matter,charge transporting material, etc. according to neccessity.

The polymer LED of the present invention comprises an light emittinglayer between the electrodes consisting of an anode and a cathode, andthe light emitting layer contains the light-emitting polymer compositionof the present invention.

Moreover, the polymer LED of the present invention comprises an lightemitting layer between the electrodes consisting of an anode and acathode, and the light emitting layer is formed by using the solutioncomposition of the present invention.

Moreover, the polymer LED of the present invention include: a polymerLED having an electron transporting layer between a cathode and a lightemitting layer; a polymer LED having an hole transporting layer betweenan anode and a light emitting layer; and a polymer LED having anelectron transporting layer between an cathode and a light emittinglayer, and a hole transporting layer between an anode and a lightemitting layer.

Specifically, the following structures a)-d) are exemplified.

a) anode/light emitting layer/cathode

b) anode/hole transporting layer/light emitting layer/cathode

c) anode/light emitting layer/electron transporting layer/cathode

d) anode/hole transporting layer/light emitting layer/electrontransporting layer/cathode

(wherein, “/” indicates adjacent lamination of layers. Hereinafter, thesame).

Herein, the light emitting layer is a layer having function to emit alight, the hole transporting layer is a layer having function totransport a hole, and the electron transporting layer is a layer havingfunction to transport an electron. Herein, the electron transportinglayer and the hole transporting layer are generically called a chargetransporting layer.

The light emitting layer, hole transporting layer and electrontransporting layer also may be used each independently in two or morelayers.

Charge transporting layers disposed adjacent to an electrode, thathaving function to improve charge injecting efficiency from theelectrode and having effect to decrease driving voltage of an device areparticularly called sometimes a charge injecting layer (hole injectinglayer, electron injecting layer) in general.

For enhancing adherence with an electrode and improving charge injectionfrom an electrode, the above-described charge injecting layer orinsulation layer having a thickness of 2 nm or less may also be providedadjacent to an electrode, and further, for enhancing adherence of theinterface, preventing mixing and the like, a thin buffer layer may alsobe inserted into the interface of a charge transporting layer and lightemitting layer.

The order and number of layers laminated and the thickness of each layercan be appropriately applied while considering light emitting efficiencyand life of the device.

In the present invention, as the polymer LED having a charge injectinglayer (electron injecting layer, hole injecting layer) provided, thereare listed a polymer LED having a charge injecting layer providedadjacent to a cathode and a polymer LED having a charge injecting layerprovided adjacent to an anode.

For example, the following structures e) to p) are specificallyexemplified.

e) anode/charge injecting layer/light emitting layer/cathode

f) anode/light emitting layer/charge injecting layer/cathode

g) anode/charge injecting layer/light emitting layer/charge injectinglayer/cathode

h) anode/charge injecting layer/hole transporting layer/light emittinglayer/cathode

i) anode/hole transporting layer/light emitting layer/charge injectinglayer/cathode

j) anode/charge injecting layer/hole transporting layer/light emittinglayer/charge injecting layer/cathode

k) anode/charge injecting layer/light emitting layer/electrontransporting layer/cathode

l) anode/light emitting layer/electron transporting layer/chargeinjecting layer/cathode

m) anode/charge injecting layer/light emitting layer/electrontransporting layer/charge injecting layer/cathode

n) anode/charge injecting layer/hole transporting layer/light emittinglayer/electron transporting layer/cathode

o) anode/hole transporting layer/light emitting layer/electrontransporting layer/charge injecting layer/cathode

p) anode/charge injecting layer/hole transporting layer/light emittinglayer/electron transporting layer/charge injecting layer/cathode

As the specific examples of the charge injecting layer, there areexemplified layers containing an conducting polymer, layers which aredisposed between an anode and a hole transporting layer and contain amaterial having an ionization potential between the ionization potentialof an anode material and the ionization potential of a hole transportingmaterial contained in the hole transporting layer, layers which aredisposed between a cathode and an electron transporting layer andcontain a material having an electron affinity between the electronaffinity of a cathode material and the electron affinity of an electrontransporting material contained in the electron transporting layer, andthe like.

When the above-described charge injecting layer is a layer containing anconducting polymer, the electric conductivity of the conducting polymeris preferably 10⁻⁵ S/cm or more and 10³ S/cm or less, and for decreasingthe leak current between light emitting pixels, more preferably 10⁻⁵S/cm or more and 10² S/cm or less, further preferably 10⁻⁵ S/cm or moreand 10¹ S/cm or less.

Usually, to provide an electric conductivity of the conducting polymerof 10⁻⁵ S/cm or more and 10³ S/cm or less, a suitable amount of ions aredoped into the conducting polymer.

Regarding the kind of an ion doped, an anion is used in a hole injectinglayer and a cation is used in an electron injecting layer. As examplesof the anion, a polystyrene sulfonate ion, alkylbenzene sulfonate ion,camphor sulfonate ion and the like are exemplified, and as examples ofthe cation, a lithium ion, sodium ion, potassium ion, tetrabutylammonium ion and the like are exemplified.

The thickness of the charge injecting layer is for example, from 1 nm to100 nm, preferably from 2 nm to 50 nm.

Materials used in the charge injecting layer may properly be selected inview of relation with the materials of electrode and adjacent layers,and there are exemplified conducting polymers such as polyaniline andderivatives thereof, polythiophene and derivatives thereof, polypyrroleand derivatives thereof, poly(phenylene vinylene) and derivativesthereof, poly(thienylene vinylene) and derivatives thereof,polyquinoline and derivatives thereof, polyquinoxaline and derivativesthereof, polymers containing aromatic amine structures in the main chainor the side chain, and the like, and metal phthalocyanine (copperphthalocyanine and the like), carbon and the like.

The insulation layer having a thickness of 2 nm or less has function tomake charge injection easy. As the material of the above-describedinsulation layer, metal fluoride, metal oxide, organic insulationmaterials and the like are listed. As the polymer LED having aninsulation layer having a thickness of 2 nm or less, there are listedpolymer LEDs having an insulation layer having a thickness of 2 nm orless provided adjacent to a cathode, and polymer LEDs having aninsulation layer having a thickness of 2 nm or less provided adjacent toan anode.

Specifically, there are listed the following structures q) to ab) forexample.

q) anode/insulation layer having a thickness of 2 nm or less/lightemitting layer/cathode

r) anode/light emitting layer/insulation layer having a thickness of 2nm or less/cathode

s) anode/insulation layer having a thickness of 2 nm or less/lightemitting layer/insulation layer having a thickness of 2 nm orless/cathode

t) anode/insulation layer having a thickness of 2 nm or less/holetransporting layer/light emitting layer/cathode

u) anode/hole transporting layer/light emitting layer/insulation layerhaving a thickness of 2 nm or less/cathode

v) anode/insulation layer having a thickness of 2 nm or less/holetransporting layer/light emitting layer/insulation layer having athickness of 2 nm or less/cathode

w) anode/insulation layer having a thickness of 2 nm or less/lightemitting layer/electron transporting layer/cathode

x) anode/light emitting layer/electron transporting layer/insulationlayer having a thickness of 2 nm or less/cathode

y) anode/insulation layer having a thickness of 2 nm or less/lightemitting layer/electron transporting layer/insulation layer having athickness of 2 nm or less/cathode

z) anode/insulation layer having a thickness of 2 nm or less/holetransporting layer/light emitting layer/electron transportinglayer/cathode

aa) anode/hole transporting layer/light emitting layer/electrontransporting layer/insulation layer having a thickness of 2 nm orless/cathode

ab) anode/insulation layer having a thickness of 2 nm or less/holetransporting layer/light emitting layer/electron transportinglayer/insulation layer having a thickness of 2 nm or less/cathode

In producing a light emitting layer, when a film is formed from asolution by using such light-emitting polymer solution composition ofthe present invention, only required is removal of the solvent by dryingafter coating of this solution, and even in the case of mixing of acharge transporting material and a light emitting material, the samemethod can be applied, causing an extreme advantage in production. Asthe film forming method from a solution, there can be used coatingmethods such as a spin coating method, casting method, micro gravurecoating method, gravure coating method, bar coating method, roll coatingmethod, wire bar coating method, dip coating method, spray coatingmethod, screen printing method, flexo printing method, offset printingmethod, inkjet printing method and the like.

Regarding the thickness of the light emitting layer, the optimum valuediffers depending on material used, and may properly be selected so thatthe driving voltage and the light emitting efficiency become optimumvalues, and for example, it is from 1 nm to 1 μm, preferably from 2 nmto 500 nm, further preferably from 5 nm to 200 nm.

In the polymer LED of the present invention, light emitting materialsother than the above light-emitting polymer can also be mixed in a lightemitting layer. Further, the light emitting layer containing lightemitting materials other than the above light-emitting polymer may alsobe laminated with a light emitting layer containing the abovelight-emitting polymer.

As the light emitting material, known materials can be used. In acompound having lower molecular weight, there can be used, for example,naphthalene derivatives, anthracene or derivatives thereof, perylene orderivatives thereof; dyes such as polymethine dyes, xanthene dyes,coumarine dyes, cyanine dyes; metal complexes of 8-hydroxyquinoline orderivatives thereof, aromatic amine, tetraphenylcyclopentane orderivatives thereof, or tetraphenylbutadiene or derivatives thereof, andthe like.

Specifically, there can be used known compounds such as those describedin JP-A Nos. 57-51781, 59-195393 and the like, for example.

When the polymer LED of the present invention has a hole transportinglayer, as the hole transporting materials used, there are exemplifiedpolyvinylcarbazole or derivatives thereof, polysilane or derivativesthereof, polysiloxane derivatives having an aromatic amine in the sidechain or the main chain, pyrazoline derivatives, arylamine derivatives,stilbene derivatives, triphenyldiamine derivatives, polyaniline orderivatives thereof, polythiophene or derivatives thereof, polypyrroleor derivatives thereof, poly(p-phenylenevinylene) or derivativesthereof, poly(2,5-thienylenevinylene) or derivatives thereof, or thelike.

Specific examples of the hole transporting material include thosedescribed in JP-A Nos. 63-70257, 63-175860, 2-135359, 2-135361,2-209988, 3-37992 and 3-152184.

Among them, as the hole transporting materials used in the holetransporting layer, preferable are polymer hole transporting materialssuch as polyvinylcarbazole or derivatives thereof, polysilane orderivatives thereof, polysiloxane derivatives having an aromatic aminecompound group in the side chain or the main chain, polyaniline orderivatives thereof, polythiophene or derivatives thereof,poly(p-phenylenevinylene) or derivatives thereof,poly(2,5-thienylenevinylene) or derivatives thereof, or the like, andfurther preferable are polyvinylcarbazole or derivatives thereof,polysilane or derivatives thereof and polysiloxane derivatives having anaromatic amine compound group in the side chain or the main chain. Inthe case of a hole transporting material having lower molecular weight,it is preferably dispersed in a polymer binder for use.

Polyvinylcarbazole or derivatives thereof are obtained, for example, bycation polymerization or radical polymerization from a vinyl monomer.

As the polysilane or derivatives thereof, there are exemplifiedcompounds described in Chem. Rev., 89, 1359 (1989) and GB 2300196published specification, and the like. For synthesis, methods describedin them can be used, and a Kipping method can be suitably usedparticularly.

As the polysiloxane or derivatives thereof, those having the structureof the above-described hole transporting material having lower molecularweight in the side chain or main chain, since the siloxane skeletonstructure has poor hole transporting property. Particularly, there areexemplified those having an aromatic amine having hole transportingproperty in the side chain or main chain.

The method for forming a hole transporting layer is not restricted, andin the case of a hole transporting layer having lower molecular weight,a method in which the layer is formed from a mixed solution with apolymer binder is exemplified. In the case of a polymer holetransporting material, a method in which the layer is formed from asolution is exemplified.

The solvent used for the film forming from a solution is notparticularly restricted providing it can dissolve a hole transportingmaterial. As the solvent, there are exemplified chlorine solvents suchas chloroform, methylene chloride, dichloroethane and the like, ethersolvents such as tetrahydrofuran and the like, aromatic hydrocarbonsolvents such as toluene, xylene and the like, ketone solvents such asacetone, methyl ethyl ketone and the like, and ester solvents such asethyl acetate, butyl acetate, ethylcellosolve acetate and the like.

As the film forming method from a solution, there can be used coatingmethods such as a spin coating method, casting method, micro gravurecoating method, gravure coating method, bar coating method, roll coatingmethod, wire bar coating method, dip coating method, spray coatingmethod, screen printing method, flexo printing method, offset printingmethod, inkjet printing method and the like, from a solution.

The polymer binder mixed is preferably that does not disturb chargetransport extremely, and that does not have strong absorption of avisible light is suitably used. As such polymer binder, polycarbonate,polyacrylate, poly(methyl acrylate), poly(methyl methacrylate),polystyrene, poly(vinyl chloride), polysiloxane and the like areexemplified.

Regarding the thickness of the hole transporting layer, the optimumvalue differs depending on material used, and may properly be selectedso that the driving voltage and the light emitting efficiency becomeoptimum values, and at least a thickness at which no pin hole isproduced is necessary, and too large thickness is not preferable sincethe driving voltage of the device increases. Therefore, the thickness ofthe hole transporting layer is, for example, from 1 nm to 1 μm,preferably from 2 nm to 500 nm, further preferably from 5 nm to 200 nm.

When the polymer LED of the present invention has an electrontransporting layer, known compounds are used as the electrontransporting materials, and there are exemplified oxadiazolederivatives, anthraquinonedimethane or derivatives thereof, benzoquinoneor derivatives thereof, naphthoquinone or derivatives thereof,anthraquinone or derivatives thereof, tetracyanoanthraquinodimethane orderivatives thereof, fluorenone derivatives, diphenyldicyanoethylene orderivatives thereof, diphenoquinone derivatives, or metal complexes of8-hydroxyquinoline or derivatives thereof, polyquinoline and derivativesthereof, polyquinoxaline and derivatives thereof, polyfluorene orderivatives thereof, and the like.

Specifically, there are exemplified those described in JP-A Nos.63-70257, 63-175860, 2-135359, 2-135361, 2-209988, 3-37992 and 3-152184.

Among them, oxadiazole derivatives, benzoquinone or derivatives thereof,anthraquinone or derivatives thereof, or metal complexes of8-hydroxyquinoline or derivatives thereof, polyquinoline and derivativesthereof, polyquinoxaline and derivatives thereof, polyfluorene orderivatives thereof are preferable, and2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole, benzoquinone,anthraquinone, tris(8-quinolinol)aluminum and polyquinoline are furtherpreferable.

The method for forming the electron transporting layer is notparticularly restricted, and in the case of an electron transportingmaterial having lower molecular weight, a vapor deposition method from apowder, or a method of film-forming from a solution or melted state isexemplified, and in the case of a polymer electron transportingmaterial, a method of film-forming from a solution or melted state isexemplified, respectively.

The solvent used in the film-forming from a solution is not particularlyrestricted provided it can dissolve electron transporting materialsand/or polymer binders. As the solvent, there are exemplified chlorinesolvents such as chloroform, methylene chloride, dichloroethane and thelike, ether solvents such as tetrahydrofuran and the like, aromatichydrocarbon solvents such as toluene, xylene and the like, ketonesolvents such as acetone, methyl ethyl ketone and the like, and estersolvents such as ethyl acetate, butyl acetate, ethylcellosolve acetateand the like.

As the film-forming method from a solution or melted state, there can beused coating methods such as a spin coating method, casting method,micro gravure coating method, gravure coating method, bar coatingmethod, roll coating method, wire bar coating method, dip coatingmethod, spray coating method, screen printing method, flexo printingmethod, offset printing method, inkjet printing method and the like.

The polymer binder to be mixed is preferably that which does notextremely disturb a charge transport property, and that does not havestrong absorption of a visible light is suitably used. As such polymerbinder, poly(N-vinylcarbazole), polyaniline or derivatives thereof,polythiophene or derivatives thereof, poly(p-phenylene vinylene) orderivatives thereof, poly(2,5-thienylene vinylene) or derivativesthereof, polycarbonate, polyacrylate, poly(methyl acrylate), poly(methylmethacrylate), polystyrene, poly(vinyl chloride), polysiloxane and thelike are exemplified.

Regarding the thickness of the electron transporting layer, the optimumvalue differs depending on material used, and may properly be selectedso that the driving voltage and the light emitting efficiency becomeoptimum values, and at least a thickness at which no pin hole isproduced is necessary, and too large thickness is not preferable sincethe driving voltage of the device increases. Therefore, the thickness ofthe electron transporting layer is, for example, from 1 nm to 1 μm,preferably from 2 nm to 500 nm, further preferably from nm to 200 nm.

The substrate forming the polymer LED of the present invention maypreferably be that does not change in forming an electrode and layers oforganic materials, and there are exemplified glass, plastics, polymerfilm, silicon substrates and the like. In the case of a opaquesubstrate, it is preferable that the opposite electrode is transparentor semitransparent.

At least one of the electrodes consisting of an anode and a cathode, istransparent or semitransparent. It is preferable that the anode istransparent or semitransparent.

As the material of this anode, electron conductive metal oxide films,semitransparent metal thin films and the like are used. Specifically,there are used indium oxide, zinc oxide, tin oxide, and compositionthereof, i.e. indium/tin/oxide (ITO), and films (NESA and the like)fabricated by using an electron conductive glass composed ofindium/zinc/oxide, and the like, and gold, platinum, silver, copper andthe like. Among them, ITO, indium/zinc/oxide, tin oxide are preferable.As the fabricating method, a vacuum vapor deposition method, sputteringmethod, ion plating method, plating method and the like are used. As theanode, there may also be used organic transparent conducting films suchas polyaniline or derivatives thereof, polythiophene or derivativesthereof and the like.

The thickness of the anode can be appropriately selected whileconsidering transmission of a light and electric conductivity, and forexample, from 10 nm to 10 μm, preferably from 20 nm to 1 μm, furtherpreferably from 50 nm to 500 nm.

Further, for easy charge injection, there may be provided on the anode alayer comprising a phthalocyanine derivative conducting polymers, carbonand the like, or a layer having an average film thickness of 2 nm orless comprising a metal oxide, metal fluoride, organic insulatingmaterial and the like.

As the material of a cathode used in the polymer LED of the presentinvention, that having lower work function is preferable. For example,there are used metals such as lithium, sodium, potassium, rubidium,cesium, beryllium, magnesium, calcium, strontium, barium, aluminum,scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium,terbium, ytterbium and the like, or alloys comprising two of more ofthem, or alloys comprising one or more of them with one or more of gold,silver, platinum, copper, manganese, titanium, cobalt, nickel, tungstenand tin, graphite or graphite intercalation compounds and the like.Examples of alloys include a magnesium-silver alloy, magnesium-indiumalloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminumalloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminumalloy and the like. The cathode may be formed into a laminated structureof two or more layers.

The thickness of the cathode can be appropriately selected whileconsidering transmission of a light and electric conductivity, and forexample, from 10 nm to 10 μm, preferably from 20 nm to 1 μm, furtherpreferably from 50 nm to 500 nm.

As the method for fabricating a cathode, there are used a vacuum vapordeposition method, sputtering method, lamination method in which a metalthin film is adhered under heat and pressure, and the like. Further,there may also be provided, between a cathode and an organic layer, alayer comprising an conducting polymer, or a layer having an averagefilm thickness of 2 nm or less comprising a metal oxide, metal fluoride,organic insulation material and the like, and after fabrication of thecathode, a protective layer may also be provided which protects thepolymer LED. For stable use of the polymer LED for a long period oftime, it is preferable to provide a protective layer and/or protectivecover for protection of the device in order to prevent it from outsidedamage.

As the protective layer, there can be used a polymeric compound, metaloxide, metal fluoride, metal borate and the like. As the protectivecover, there can be used a glass plate, a plastic plate the surface ofwhich has been subjected to lower-water-permeation treatment, and thelike, and there is suitably used a method in which the cover is pastedwith an device substrate by a thermosetting resin or light-curing resinfor sealing. If space is maintained using a spacer, it is easy toprevent an device from being injured. If an inner gas such as nitrogenand argon is sealed in this space, it is possible to prevent oxidationof a cathode, and further, by placing a desiccant such as barium oxideand the like in the above-described space, it is easy to suppress thedamage of an device by moisture adhered in the production process. Amongthem, any one means or more are preferably adopted.

In the devices of the present invention, preferable is a device which isproduced by heat-treating at a temperature of 50° C. or more, during orafter the light emitting layer is formed, in view of life time of thedevices.

The condition of heat-treating is usually a condition where an oniumsalt is decomposed by heat-treating. The heat-treating temperature is50° C. or more, and preferably, it is in a range of 50° C. to 300° C.The heat-treating time is usually from about 1 second to 24 hours.

The heat-treating can be performed using, for example, a hot plate, anoven, an infrared lamp, etc. The heat-treating may be under reducedpressure.

As for the heat-treating, it is preferable to carry out it after forminga light emitting layer, and more preferably, just after forming a lightemitting layer.

Furthermore, the device of the present invention may be produced byradiation exposure during or after the light emitting layer is formed.As the radiation, for example, ultraviolet ray, electron beam, and X-rayare exemplified, and ultraviolet ray is preferable.

The polymer LED of the present invention can be used for a flat lightsource, a segment display, a dot matrix display, and a liquid crystaldisplay as a back light, etc.

For obtaining light emission in plane form using the polymer LED of thepresent invention, an anode and a cathode in the plane form may properlybe placed so that they are laminated each other. Further, for obtaininglight emission in pattern form, there is a method in which a mask with awindow in pattern form is placed on the above-described plane lightemitting device, a method in which an organic layer in non-lightemission part is formed to obtain extremely large thickness providingsubstantial non-light emission, and a method in which any one of ananode or a cathode, or both of them are formed in the pattern. Byforming a pattern by any of these methods and by placing some electrodesso that independent on/off is possible, there is obtained a displaydevice of segment type which can display digits, letters, simple marksand the like. Further, for forming a dot matrix device, it may beadvantageous that anodes and cathodes are made in the form of stripesand placed so that they cross at right angles. By a method in which aplurality of kinds of polymeric compounds emitting different colors oflights are placed separately or a method in which a color filter orluminescence converting filter is used, area color displays and multicolor displays are obtained. A dot matrix display can be driven bypassive driving, or by active driving combined with TFT and the like.These display devices can be used as a display of a computer,television, portable terminal, portable telephone, car navigation, viewfinder of a video camera, and the like. Further, the above-describedlight emitting device in plane form is a thin self-light-emitting one,and can be suitably used as a flat light source for back-light of aliquid crystal display, or as a flat light source for illumination.Further, if a flexible plate is used, it can also be used as a curvedlight source or a display.

Hereafter, in order to explain the present invention in detail withshowing examples, but the present invention is not limited to these.

Here, about the number average molecular weight, the polystyrene reducednumber average molecular weight was obtained by gel permeationchromatography (GPC) using chloroform or tetrahydrofuran as a solvent.

SYNTHETIC EXAMPLE 1 (SYNTHESIS OF COMPOUND A)

Inside of a 300 ml eggplant type flask was replaced by nitrogen, 5.00 gof tris(pentafluorophenyl)borane was dissolved in 200 ml dehydrateddiethyl ether, and 0.31 g of potassium cyanide was added. Afterrefluxing for 3 hours, the solvent was distilled off and 5.71 g ofCompound A was obtained.

MS(ESI-negative)

m/z 1049.8([M-K]⁻)K⁺|(C₆F₅)₃B≡N—B(C₆F₅)₃|⁻  A

EXAMPLE 2 (SYNTHESIS OF COMPOUND B)

Inside of a 25 ml Schlenk tube was replaced by nitrogen,1,1′-dimethyl-4,43-bipyridinium dichloride 40 mg was dissolved in 4.0 mlwater, and Compound A 400 mg was added. 4.0 ml of chloroform was added,and stirred for 4.5 hours. After being filtrated and washed, the solventwas distilled off, and 288 mg of Compound B was obtained.

¹H-NMR (300 MHz, DMSO-d₆)

δ 9.30 (4H, brs), 8.78 (4H, brs), 4.47 (6H, s)

EXAMPLE 3 (SYNTHESIS OF COMPOUND C)

Inside of a 25 ml Schlenk tube was substituted by nitrogen,bis(4-t-butylphenyl)iodonium triflate 150 mg was suspended in 4 mlwater. Compound A 392 mg was added, and further toluene 3 ml was added,then the insoluble material was dissolved. After 8 hours' stirring,being partitioned and the aqueous phase was extracted with toluene.After being dried by sodium sulfate, the solvent was distilled off, and373 mg Compound C was obtained.

¹H-NMR (DMSO-d₆, 300 MHz)

δ 8.16 (4H, d), 7.55 (4H, m), 1.26 (18H, s)

¹⁹F-NMR (DMSO-d₆, 300 MHz)

δ −132.5, −133.6, −134.1, −157.8, −159.7, −164.1, −165.2

SYNTHETIC EXAMPLE 4 (SYNTHESIS OF COMPOUND D)

Inside of a 25 ml Schlenk tube was replaced by nitrogen,triphenylsulfonium bromide 100 mg was dissolved in 4 ml water. Thesolution became cloudy when Compound A 408 mg was added. After 8 hoursstirring with 3 ml toluene addition, being partitioned and the aqueousphase was extracted with toluene and diethyl ether. After being driedwith sodium sulfate, the solvent was distilled off, and 449 mg CompoundD was obtained.

¹H-NMR (DMSO-d₆, 300 MHz)

δ 7.90-7.75 (15H, m)

¹⁹F-NMR (DMSO-d₆, 300 MHz)

δ −132.7, −133.7, −134.1, −157.9, −160.0, −164.2, −165.3

SYNTHETIC EXAMPLE 5

<Synthesis of Light-Emitting Polymer 1>

2,7-dibromo-9,9-dioctylfluorene (26 g, 0.047 mol),2,7-dibromo-9,9-diisopentylfluorene (5.6 g, 0.012 mol), and2,2′-bipyridyl (22 g, 0.141 mol) were dissolved in dehydratedtetrahydrofuran 1600 mL, and the inside of the system was replaced bynitrogen bubbling. Under nitrogen atmosphere, to this solution,bis(1,5-cyclooctadiene)Ni(0){Ni(COD)₂} (40 g, 0.15 mol) was added, andthe temperature was raised to 60° C., and reacted for 8 hours. After thereaction, the reaction mixture was cooled to room temperature (about 25°C.), added dropwise into a mixed solution of 25% aqueous ammonia 200ml/methanol 1200 ml/ion-exchanged water 1200 ml, and stirred for about30 minutes. The deposited precipitate was filtrated, and air-dried.After being dissolved in toluene 1100 mL, it was filtrated, and thefiltrated solution was added dropwise in methanol 3300 mL, and wasstirred for 30 minutes. The deposited precipitate was filtrated andwashed by methanol 1000 mL, then dried under reduced-pressure for 5hours. The yield of a resultant copolymer was 20 g (hereafter referredto as Light-emitting Polymer 1). The polystyrene reduced number averagemolecular weight and weight average molecular weight of Light-emittingPolymer 1 were Mn=9.9×10⁴ and Mw=2.0×10⁵, respectively, (mobile-phase:chloroform).

SYNTHETIC EXAMPLE 6

<Synthesis of 4-t-butyl-2,6-dimethylbromobenzene>

Under an inert atmosphere, 225 g of acetic acid was charged into a 500ml three-necked flask, and 24.3 g of 5-t-butyl-m-xylene was added. Then,after adding 31.2 g of bromine, reaction was conducted at 15-20° C. for3 hours.

The reaction liquid was added to 500 ml of water, and the depositedprecipitate was filtrated. Washing with 250 ml of water twice and 34.2 gof white solid was obtained.

¹H-NMR(300 MHz/CDCl₃):

δ (ppm)=1.3 [s,9H], 2.4 [s,6H], 7.1 [s,2H]

MS(FD⁺)M⁺ 241

SYNTHETIC EXAMPLE 7

<Synthesis ofN,N′-diphenyl-N,N′-bis(4-t-butyl-2,6-dimethylphenyl)-1,4-phenylenediamine>

Under an inert atmosphere, deaerated and dehydrated toluene 36 ml wascharged in a 10 ml three-necked flask, and 0.63 g oftri(t-butyl)phosphine was added. Then, 0.41 g oftris(dibenzylidineacetone)dipalladium, 9.6 g of the above4-t-butyl-2,6-dimethylbromobenzene, 5.2 g of t-butoxy sodium, and 4.7 gof N,N′-diphenyl-1,4-phenylene diamine were added, and reacted at 100°C. for 3 hours.

The reaction liquid was added to 300 ml of saturated NaCl aqueoussolution, and extracted by chloroform 300 ml warmed at about 50 r. Afterdistilling off the solvent, toluene 100 ml was added and heated untilthe solid was dissolved. After standing to cool, precipitate wasfiltrated and 9.9 g of white solid was obtained.

SYNTHETIC EXAMPLE 8

<Synthesis ofN,N′-bis(4-bromophenyl)-N,N′-bis(4-t-butyl-2,6-dimethylphenyl)-1,4-phenylenediamine>

Uunder an inert atmosphere, dehydrated N,N-dimethylformamide 350 ml wascharged into a 1000 ml three-necked flask and 5.2 g of the aboveN,N′-diphenyl-N,N′-bis(4-t-butyl-2,6-dimethylphenyl)-1,4-phenylenediaminewas dissolved, then 3.5 g of N-bromosuccinimide/andN,N-dimethylformamide solution was added dropwise, and the reaction wasconducted one whole day and night with colling by an ice bath.

150 ml of water was added to the reaction liquid, and the depositedprecipitate was filtrated, it washed twice by methanol 50 ml, and 4.4 gof white solid was obtained.

¹H-NMR(300 MHz/THF-d8):

δ (ppm)=1.3 [s,18H], 2.0 [s,12H], 6.6 to 6.7 [d,4H], 6.8 to 6.9 [br,4H],7.1 [s,4H], 7.2 to 7.3 [d,4H]

MS(FD⁺)M⁺ 738

SYNTHETIC EXAMPLE 9

<Synthesis of Light-Emitting Polymer 2>

The above 2,7-dibromo-3,6-dioctyloxydibenzothiophene (5.4 g, 9 mmol,synthesized according to JP-A-2004-002703), the aboveN,N′-bis(4-bromophenyl)-N,N′-bis(4-t-butyl-2,6-dimethylphenyl)-1,4-phenylene diamine (4.5 g, 6 mmol), and2,2′-bipyridyl (5.1 g, 33 mmol) were dissolved in tetrahydrofuran 420mL, and the inside of the system was replaced by nitrogen with nitrogenbubbling. Under nitrogen atmosphere, into the solution,bis(1,5-cyclooctadiene)Ni(0){Ni(COD)₂} (9.0 g, 33 mmol) was added, andraised the temperature to 60° C., and reacted for 3 hours with stirring.After the reaction, the reaction mixture was cooled to room temperature(about 25° C.), added dropwise into a mixed solution of 25% aqueousammonia 150 ml/methanol 1500 ml/ion-exchanged water 600 ml, and stirredfor 1 hour. The deposited precipitate was filtrated, and dried underreduced pressure for 2 hours, and then dissolved in toluene 450 mL.Then, 1N hydrogen-chloride 450 mL was added, and stirred for 1 hour, theaqueous layer was removed, 4% aqueous ammonia 450 mL was added to theorganic layer, and after stirring for 1 hour, the aqueous layer wasremoved. The organic layer was added dropwise to methanol 1350 mL, andstirred for 1 hour, and the deposited precipitate was filtrated anddried under reduced-pressure for 2 hours, and dissolved in toluene 400mL. Then, purification through alumina column (amount alumina of 100 g)was performed, and the collected toluene solution was added dropwise tomethanol 1350 mL, stirred for 1 hour, the deposited precipitate was anddried under reduced-pressure for 2 hours.

The yield of the resultant copolymer (hereafter referred to asLight-emitting Polymer 2) was 5.5 g. The polystyrene reduced numberaverage molecular weight and the weight average molecular weight wereMn=3.0×10⁴ and Mw=1.8×10⁵, respectively, (mobile-phase:chloroform).

SYNTHETIC EXAMPLE 10

SYNTHETIC EXAMPLE 11

Compound P

Under an inert atmosphere, into a 300 ml three-necked flask,1-naphthalene boronic acid 5.00 g (29 mmol), 2-bromobenzaldehyde 6.46 g(35 mmol), potassium carbonate 10.0 g (73 mmol), toluene 36 ml, andion-exchanged water 36 ml, were added, and argon bubbling was carriedout for 20 minutes at room temperature, with stirring. Then,tetrakis(triphenyl phosphine)Pd 16.8 mg (0.15 mmol) was added, and argonbubbling was carried out for 10 minutes at room temperature, withstirring further. The temperature was raised to 100° C., and reacted for25 hours. After cooling to room temperature, the organic layer wasextracted with toluene, dried with sodium sulfate, and then the solventwas distilled off. By purification through silica gel column, with amixed solvent of toluene:cyclohexane=1:2 as eluent, 5.18 g (86% ofyield) of Compound P was obtained as white crystal.

¹H-NMR(300 MHz/CDCl₃):

δ 7.39-7.62 (m, 5H), 7.70 (m, 2H), 7.94 (d, 2H), 8.12 (dd, 2H), 9.63 (s,1H)

MS(APCI(+)):(M+H)+233

SYNTHETIC EXAMPLE 11

Under an inert atmosphere, 8.00 g (34.4 mmol) of Compound P anddehydrated THF 46 ml were charged into a 300 ml three-necked flask, andit was cooled to −78 r. Then, n-octyl magnesium bromide (1.0 mol/lTHFsolution) 52 ml was added dropwise for 30 minutes. After the dropwiseaddition, the temperature was raised to 0° C., and after being stirredfor 1 hour, the temperature was raised to room temperature and stirredfor 45 minutes. In an ice bath, the reaction was terminated by adding 20ml of 1N hydrogen chloride, and the organic layer was extracted withethyl acetate, and dried with sodium sulfate.

After distilling off the solvent, by purifying through silica gel columnwith toluene:hexane=10:1 mixed solvent as the eluent, 7.64 g (64% ofyield) of Compound Q was obtained as light yellow oil. Two peaks wereobserved by HPLC measurement, but these were the same mass number byLC-MS measurement, and it was regarded as a mixture of isomers.

SYNTHETIC EXAMPLE 12

Under an inert atmosphere, into a 500 ml three-necked flask, 5.00 g(14.4 mmol) of compound Q (mixture of anisomer), and 74 ml of dehydrateddichloromethane were added, and dissolved with stirring at roomtemperature. Then, at room temperature, etherate complex of borontrifluoride was added dropwise for 1 hour, and after the addition,stirred for 4 hours at room. Ethanol 125 ml was added slowly withstirring, and after termination of heat generation, the organic layerwas it extracted with chloroform, washed with water 2 times, and driedwith magnesium sulfate.

After distilling off the solvent, by purifying through silica gel columnwith hexane solvent as the eluent, 3.22 g (68% of yield) of Ccompound Rwas obtained as colorless oil.

¹H-NMR(300 MHz/CDCl₃):

δ0.90 (t, 3H), 1.03 to 1.26 (m, 14H), and 2.13 (m - -) 2H, 4.05 (t, 1H),7.35 (dd, 1H), 7.46 to 7.50 (m, 2H), 7.59 to 7.65 (m, 3H), 7.82 (d, 1H),7.94 (d, 1H), 8.35 (d, 1H), 8.75 (d, 1H) MS(APCI(+)):(M+H)⁺ 329

SYNTHETIC EXAMPLE 13

Under an inert atmosphere, in a 200 ml three-necked flask, 20 ml ofion-exchanged water was charged, and 18.9 g (0.47 mols) of sodiumhydroxide was added portionally with stirring, and dissolved. After thesolution was cooled to room temperature, toluene 20 ml, 5.17 g (15.7mmol) of compound R, and 1.52 g (4.72 mmol) of bromotributyl ammoniumwere added, and the temperature wase raised to 50° C. n-octylbromide wasadded dropwise, and after the dropping addition, reacted at 50° C. for 9hours. After the reaction, the organic layer was extracted with toluene,and washed with water twice, and dried by sodium sulfate. By purifyingthrough silica gel column with hexane solvent as the eluent, 5.13 g (74%of yield) of Compound S was obtained as yellow oil.

¹H-NMR(300 MHz/CDCl₃):

δ 0.52 (m, 2H), 0.79 (t, 6H), and 1.00 to 1.20 (m - -) 22H, 2.05 (t,4H), 7.34 (d, 1H), 7.40 to 7.53 (m, 2H), 7.63 (m, 3H), 7.83 (d, 1H),7.94 (d, 1H), 8.31 (d, 1H), 8.75 (d, 1H)

MS(APCI(+)):(M+H)⁺ 441

SYNTHETIC EXAMPLE 14

Under air atmosphere, in a 50 ml three-necked flask, 4.00 g (9.08 mmol)of Compound S, and a mixed solvent 57 ml ofacetic-acid:dichloromethane=1:1 were charged, and dissolved withstirring at room temperature. Then, tribromobenzyl-trimethylammonium7.79 g (20.0 mmol) was added with stirring, and zinc chloride was addeduntil tribromobenzyl-trimethylammonium was completely dissolved. After20 hours stirring at room temperature, the reaction was terminated byadding 10 ml of 5% aqueous sodium-hydrogensulfite solution, the organiclayer was extracted with chloroform, washed with aqueous potassiumcarbonate solution twice, and dried with sodium sulfate.

After purifying through a flash column twice with hexane as the eluent,by recrystallization with a mixed solvent of ethanol:hexane=1:1, andthenethanol:hexane=10:1, 4.13 g (76% of yield) of Compound T wasobtained as a white crystal.

¹H-NMR(300 MHz/CDCl₃):

δ 0.60 (m, 2H), 0.91 (t, 6H), 1.01 to 1.38 (m, 22H), 2.09 (t, 4H), 7.62to 7.75 (m, 3H), 7.89 (s, 1H), 8.20 (d, 1H), 8.47 (d, 1H), 8.72 (d, 1H)

MS(APPI(+)):(M+H)⁺ 598

SYNTHETIC EXAMPLE 1

<Synthesis of Light-Emitting Polymer 3>

After dissolving Compound T (8.0 g) and 2,2′-bipyridyl (5.9 g) intetrahydrofuran 300 mL, the inside of the system was replaced bynitrogen with nitrogen bubbling. Under nitrogen atmosphere, thissolution was raised to 60 AC, bis(1,5-cyclo octadiene)Ni(0){Ni(COD)₂}(10.4 g, 0.038 mol) was added and reacted for 5 hours. After thereaction, this reaction liquid was cooled to room temperature (about 25°C.), and added dropwise into a solution mixture of 25% aqueous ammonia40 mL/methanol 300 mL/ion-exchanged water 300 mL, after stirring for 30minutes, the deposited precipitate was air-dried. Then, after beingdissolved in toluene 400 mL, it was filtrated and the filtrated solutionwas purified through an alumina column. About 300 mL of 1Nhydrogen-chloride was added, and stirred for 3 hours, the aqueous layerwas removed, about 300 mL of 4% aqueous ammonia was added to thenorganic layer, and the aqueous layer was removed after stirring for 2hours. After about 300 mL of ion-exchanged-water was added to theorganic layer and stirred for 1 hour, the aqueous layer was removed.After about 100 mL of methanol was added dropwise to the organic layer,stirred for 1 hour and allowed to stand, supernatant layer liquid wasremoved by decantation. The resultant precipitate was dissolved intoluene 100 mL, and it was added dropwise to about 200 mL of methanol,stirred for 1 hour, filtrated, and dried under reduced-pressure for 2hours. The yield of the resultant copolymer was 4.1 g (hereafterreferred to as Light-emitting Polymer 3). The polystyrene reduced numberaverage molecular weights and the weight average molecular weight ofLight-emitting Polymer 3 were Mn=1.5×10⁵ and Mw=2.7×10⁵, respectively,(mobile-phase:tetrahydrofuran).

SYNTHETIC EXAMPLE 16

<Synthesis of Light-Emitting Polymer 4>

After dissolving Compound T (0.65 g) and N,N′-bis(4-bromophenyl)-N,N′-bis(4-t-butyl-2,6-dimethylphenyl)-1,4-phenylene diamine(0.34 g) and 2,2′-bipyridyl (0.58 g) in tetrahydrofuran 100 mL, theinside of the system was replaced by nitrogen with nitrogen bubbling.Under nitrogen atmosphere, bis(1,5-cyclo octadiene)Ni(0){Ni(COD)₂} (10.4g, 0.038 mol) was added, raised the temperature to 60° C., and reactedfor 3 hours with stirring. After the reaction, this reaction liquid wascooled to room temperature (about 25° C.), and added dropwise into asolution mixture of 25% aqueous ammonia 10 mL/methanol 100mL/ion-exchanged water 100 mL, after stirring for 1 hour, the depositedprecipitate was dried for 6 hours under reduced pressure. Then, afterbeing dissolved in toluene 50 mL, it was filtrated and the filtratedsolution was purified through an alumina column. About 50 mL of aqueousammonia was added, and stirred for 2 hours, the aqueous layer wasremoved. After about 50 mL of ion-exchanged-water was added to theorganic layer and stirred for 1 hour, the aqueous layer was removed.After about 100 mL of methanol was added dropwise to the organic layer,stirred for 1 hour and allowed to stand, supernatant layer liquid wasremoved by decantation. The resultant precipitate was dissolved intoluene 50 mL, and it was added dropwise to about 200 mL of methanol,stirred for 1 hour, filtrated, and dried under reduced-pressure for 2hours. The yield of the resultant copolymer was 390 mg (hereafterreferred to as Light-emitting Polymer 4). The polystyrene reduced numberaverage molecular weights and the weight average molecular weight ofLight-emitting Polymer 4 were Mn=1.6×10⁴ and Mw=7.4×10⁴, respectively,(mobile-phase:tetrahydrofuran).

SYNTHETIC EXAMPLE 17 (SYNTHESIS OF COMPOUND E)

Inside of a 200 ml four-necked flask was replaced with nitrogen, 0.486 gof tri(4-t-butylphenylsulfonium)trifluoro methane sulfonate, Compound A0.873 g, ion-exchanged water 20 ml, and diethylether 60 ml were charged.After equipping with stirring blade, thermometer, and condenser, it wasreacted at 21-23° C. for 16 hours. After the reaction, the contents ofthe flask were put into a 200 ml separatory funnel, and the aqueouslayer was separated. The ether layer was washed 3 times by 30 ml ofion-exchanged water. The ether layer was put in a 200 ml Erlenmeyerflask, anhydrous sodium sulfate was added to dehydrate, and anhydroussodium sulfate was filtrated of f. The ether layer was condensed at roomtemperature by evaporator, and dried until it became to a constantweight by a vacuum pump at 70-75° C. 1.19 g of Compound E was obtained.

¹H-NMR (300 MHz, DMSO-d₆)

δ 7.78 (12H,m), 1.32 (27H, s)

EXAMPLE 18 (SYNTHESIS OF COMPOUND F)

Inside of a 50 ml four-necked flask was replaced with nitrogen, 0.309 gof poly(1-n-butyl-4-vinylpyridinium trifluoromethanesulfoneimide),Compound A 1.088 g, and dimethylformamide 30 ml were charged. Afterequipping with stirring blade, thermometer, and condenser, it wasreacted at 21-23° C. for 16 hours. After the reaction, the contents ofthe flask were put into a 200 ml separatory funnel, 90 ml of toluene wasadded, and DMF was extracted with 50 ml of ion-exchanged water. Thetoluene layer was washed 3 times by 50 ml of ion-exchanged water. Thetoluene layer was put in a 200 ml Erlenmeyer flask, anhydrous sodiumsulfate was added to dehydrate, and anhydrous sodium sulfate wasfiltrated off. The toluene layer was condensed at room temperature byevaporator, and dried until it became to a constant weight by a vacuumpump at 70-75° C. 1.08 g of Compound F was obtained.

¹H-NMR (300 MHz, DMSO-d₆)

δ 5.8, 7.4, 9.1

¹⁹F-NMR (300 MHz, DMSO-d₆)

δ −132.7, −133.6, −134.8, −157.7, −159.8, −162.5, −164.0, −165.2, −166.0

SYNTHETIC EXAMPLE 19 (SYNTHESIS OF COMPOUND G)

Synthesis of Potassium Salt

Inside of a 200 ml four-necked flask was replaced with nitrogen,K₂[Ni(CN)₄] 3.01 g, tris(pentafluorophenyl)borane 25.5 g, anddiethylether 100 ml were charged. After equipping with stirring blade,thermometer, and condenser, it was reacted at 21-23° C. for 16 hours.The deposited crystal was filtrated and the cake was washed with 100 mlof ethyl acetate. The residue K₂[Ni(CN)₄] on the filter was treated by5% sodium hypochlorite. The filtrated solution was moved to a 500 mlseparatory funnel, and it was washed with 100 ml of ion-exchanged water3 times. The organic layer was moved to a 500 ml Erlenmeyer flask,anhydrous sodium sulfate was added to dehydrate, and anhydrous sodiumsulfate was filtrated off. The solvent was condensed by an evaporatorand 31.4 g of crude cake was obtained. Diethylether 60 ml and n-hexane120 ml were added to the crude cake, and stirred for 2 hours, filtrated,and the cake was washed by n-hexane 50 ml. It was dried until it becamea constant weight by drying under reduced-pressure at 70-75° C. 24.4 gof potassium salt was obtained.

SYNTHETIC EXAMPLE 20 (SYNTHESIS of COMPOUND G)

Inside of a 200 ml four-necked flask was replaced with nitrogen,potassium salt 3.0 g, diethyl ether 100 ml and ion-exchanged water 20 mlwere charged, and equipped with a stirring blade, thermometer, andcondenser. With stirring at 21-23° C., 1% hydrogen chloride 15 g wasadded dropwise in 10 minutes, and then stirred for 1 hour.

The contents of the flask were put into a 200 ml separatory funnel, andthe aqueous layer was separated. The ether layer was washed 3 times byion-exchanged water. The ether layer was put in a 200 ml Erlenmeyerflask, anhydrous sodium sulfate was added to dehydrate, and anhydroussodium sulfate was filtrated off. The ether layer was condensed at roomtemperature by evaporator, and dried until it became to a constantweight by a vacuum pump at 70-75° C. 2.81 g of Compound G was obtained.

¹⁹F-NMR (300 MHz, DMSO-d₆)

δ −132.7, −133.7, −134.3, −154.8, −157.8, −159.2, −161.0, −162.9,−164.3, −165.4, −165.8, −166.5

EXAMPLE 21 (SYNTHESIS OF COMPOUND H)

Inside of a 200 ml four-necked flask was replaced with nitrogen,1,1′-di-2-ethylhexyl-4,4′-bipyridinium diiodide 0.323 g, Compound A1.223 g, ion-exchanged water 20 ml, and diethyl ether 60 ml werecharged. After equipping with stirring blade, thermometer, andcondenser, it was reacted at 21-23° C. for 22 hours.

The contents of the flask were put into a 200 ml separatory funnel, andthe aqueous layer was separated. The ether layer was washed 3 times by40 ml ion-exchanged water. The ether layer was put in a 200 mlErlenmeyer flask, anhydrous sodium sulfate was added to dehydrate, andanhydrous sodium sulfate was filtrated off. The ether layer wascondensed at room temperature by evaporator. Tolune 50 ml was added toit, stirred at 60-65° C. for 0.5 hours, and after cooling, it wasfiltrated. The washing procedure was repeated 3 times, dried until itbecame to a constant weight by a vacuum pump at 80-85° C. 1.15 gCompound H was obtained.

¹H-NMR (270 MHz, CD₃OD)

δ 9.258 (4H, m), 8.687 (4H, m), 4.665 (4H, d), 2.049 (2H, m),

SYNTHETIC EXAMPLE 22 (SYNTHESIS of COMPOUND I)

Synthesis of Quarternary Salt

Inside of a 50 ml four-necked flask was replaced with nitrogen, 27.4 gof 1,8-diazabicyclo[5,4,0]undeca-7-ene and 11.6 g of n-octyl bromidewere charged. After equipping with stirring blade, thermometer, andcondenser, it was reacted at 21-23° C. for 22 hours. After equippingwith stirring blade, thermometer, and condenser, it was reacted at110-115° C. for 5.5 hours. After cooling to 80° C., toluene 50 ml andhexane 150 ml were charged, and it was cooled to 5° C. It was stirredbelow 5° C. for 1 hour, and allowed to stand at this temperature,supernatant layer liquid was removed by decantation. Toluene 50 ml andhexane 150 ml were charged into the flask and stirred at 60-65° C. for 1hour, it was cooled to 5° C. It was stirred below 5° C. for 1 hour, andallowed to stand at this temperature, supernatant layer liquid wasremoved by decantation. This procedure was repeated again, and theresidual solvent was distilled off by evaporator. Next, it was dried tobecome a constant weight by a vacuum pump at 80-85° C., and 19.5 g of aquarternary salt was obtained.

Quarternary salt ¹H-NMR (270 MHz, CD₃OD)

δ 3.676 (2H, m), 3.545 (6H, m), 2.054 (2H, m), 1.722(10H, m) 1.332 (10H,m), 0.798 (3H, m)

SYNTHETIC EXAMPLE 23 (SYNTHESIS OF COMPOUND I)

Inside of a 200 ml four-necked flask was replaced with nitrogen, 0.590 gof quarternary salt, 1.240 of Compound A, 20 ml of ion exchanged water,and diethyl ether 60 ml were charged. After equipping with stirringblade, thermometer, and condenser, it was reacted at 21-23° C. for 24hours. After the reaction, the contents of the flask were put into a 200ml separatory funnel, the aqueous layer was removed, and the ether layerwas washed 3 times by 40 ml of ion-exchanged water.

The ether layer was put in a 200 ml Erlenmeyer flask, anhydrous sodiumsulfate was added to dehydrate, and anhydrous sodium sulfate wasfiltrated off. The ether layer was condensed by evaporator, and drieduntil it became to a constant weight by a vacuum pump at 80-85° C. 1.53g Compound I was obtained.

Compound I ¹H-NMR (270 MHz, CD₃OD)

δ 3.660 (2H, m), 3.520 (6H, m), 2.064 (2H, m), 1.748(10H, m) 1.296 (10H,m), 0.867 (3H, m)

EXAMPLE 24 (SYNTHESIS OF COMPOUND K)

Inside of a 200 ml four-necked flask was replaced with nitrogen, 0.318 gof 1,1′-di-2-ethylhexyl-4,4′-bipyridinium diiodide, 1.144 g potassiumsalt obtained by Synthetic Example 12 of Compound G, 20 ml ofion-exchanged water, and 60 ml of diethyl ether were charged. Afterequipping with stirring blade, thermometer, and condenser, it wasreacted at 21-23° C. for 18 hours. After the reaction, the contents ofthe flask were put into a 200 ml separatory funnel, 50 ml of ethylacetate was added to it, and the aqueous layer was removed. Next, theorganic layer was washed 3 times by 30 ml of ion-exchanged water. Theorganic layer was put in a 200 ml Erlenmeyer flask, anhydrous sodiumsulfate was added to dehydrate, and anhydrous sodium sulfate wasfiltrated off. The organic layer was condensed by evaporator, and drieduntil it became to a constant weight by a vacuum pump at 80-85° C. 1.18g Compound K was obtained.

¹H-NMR (270 MHz, DMSO-d₆)

δ 9.385 (4H, d), 8.805 (4H, d), 4.634 (4H, m), 2.073(2H, m) 1.300 (16H,m), 0.870 (12H, m)

EXAMPLE 25 (SYNTHESIS OF COMPOUND L)

Inside of a 200 ml four-necked flask was replaced with nitrogen, 0.205 gof 1,1′-dibenzyl-4,4′-bipyridinium dichloride, 1.089 g of Compound A, 20ml of ion-exchanged water, and 60 ml of diethyl ether were charged.After equipping with stirring blade, thermometer, and condenser, it wasreacted at 21-23° C. for 18 hours. After the reaction, the contents ofthe flask were put into a 200 ml separatory funnel, and the aqueouslayer was removed. Next, the ether layer was washed 3 times by 30 ml ofion-exchanged water. The ether layer was put in a 200 ml Erlenmeyerflask, anhydrous sodium sulfate was added to dehydrate, and anhydroussodium sulfate was filtrated off. The ether layer was condensed byevaporator, and dried until it became to a constant weight by a vacuumpump at 80-85° C. 1.21 g Compound L was obtained.

¹H-NMR (270 MHz, DMSO-d₆)

δ 9.501 (4H, d), 8.733 (4H, d), 7.606 (4H, m), 7.479 (6H, m)

EXAMPLE 26 (SYNTHESIS OF Compound M)

Inside of a 200 ml four-necked flask was replaced with nitrogen, 0.595 gof tri(4-t-butylphenylsulfonium)trifluoromethane sulfonate, 1.144 g ofpotassium salt obtained by Synthetic Example 12 of Compound G, 20 ml ofion-exchanged water, and 60 ml of diethyl ether were charged. Afterequipping with stirring blade, thermometer, and condenser, it wasreacted at 21-23° C. for 16 hours. After the reaction, the contents ofthe flask were put into a 200 ml separatory funnel, 50 ml of ethylacetate was added to it, and the aqueous layer was removed. Next, theorganic layer was washed 3 times by 30 ml of ion-exchanged water. Theorganic layer was put in a 200 ml Erlenmeyer flask, anhydrous sodiumsulfate was added to dehydrate, and anhydrous sodium sulfate wasfiltrated off. The organic layer was condensed by evaporator, and drieduntil it became to a constant weight by a vacuum pump at 80-85° C. 1.24g compound M was obtained.

¹H-NMR (300 MHz, DMSO-d₆)

δ 7.774 (12H,m), 1.313 (27H, s)

SYNTHETIC EXAMPLE 27 (SYNTHESIS OF COMPOUND N)

Inside of a 200 ml four-necked flask was replaced with nitrogen, 1.089 gof Compound A, 20 ml of ion-exchanged water, and 50 ml of diethyl etherwere charged. After equipping with stirring blade, thermometer, andcondenser, 1% hydrochloric acid was added dropwise in 10 minutes withstirring. After 2 hours, the contents of the flask were put into a 200ml separatory funnel, and the aqueous layer was removed. Next, the etherlayer was washed 3 times by 30 ml of ion-exchanged water. The etherlayer was put in a 200 ml Erlenmeyer flask, anhydrous sodium sulfate wasadded to dehydrate, and anhydrous sodium sulfate was filtrated off. Theorganic layer was condensed by evaporator, and dried until it became toa constant weight by a vacuum pump at 80-85° C. 1.06 g Compound N wasobtained.

¹⁹F-NMR (300 MHz, DMSO-d₆)

δ −132.7, −133.7, −134.3, −154.8, −157.8, −159.2, −161.0, −162.9,−164.3, −165.4, −165.8, −166.5

<Preparation 1 of Light-Emitting Polymer Solution Composition>

25:75 (weight ratio) mixture of Light-emitting Polymer 1 andLight-emitting Polymer 2 was dissolved in a mixed solvent oftoluene/ethyl acetate=80/20 (weight ratio) in an amount to be 0.9 wt %,and further an ion pair was mixed in an amount as shown in Table 1 anddissolved. Then, it was filtrated through Teflon (registered trademark)filter having 0.2μ diameter and a coating solution was prepared. As theion pair, those of Synthetic Examples were used. Adding amount of theion pair is shown as the weight part to 100 parts by weight of the wholelight-emitting polymer.

<Preparation of a Device, and Evaluation>

On a glass substrate on which ITO film was formed in a thickness of 150nm by sputtering method, a film was formed by a thickness of 70 nm witha spin coat using a solution (Bayer Co., Baytron) ofpoly(ethylenedioxythiophene)/polystyrene sulfonic acid, and then it wasdried at 200° C. for 10 minutes on a hot plate. Next, a film of about 85nm thicknes was formed by spin-coating at a rotational rate of 1000 rpm,using the prepared coating solution of light-emitting polymer.

Furthermore, after drying this at 90° C. under reduced pressure for 1hour, a polymer LED was fabricated, by depositing 1 nm of LiF as thecathode buffer layer, 5 nm of calcium as the cathode, and subsequently,100 nm of aluminum. Here, all of the vacuum degree at the time ofdeposition were 1 to 9×10⁻⁵ Torr.

By applying a voltage to the resultant device, EL luminescence from alight emitting polymer was observed. Characteristics of the resultantdevice are shown in Table 1.

As the life-time test, luminance was measured about device having a 2mm×2 mm (area 4 mm²) light-emitting part, with conducting a 10 mAconstant current driving.

2000 cd/m² conversion life time is defined as that converted to a lifetime at the time of the initial luminance of 2000 cd/m² driving, withassuming the relation of half life-time∝(initial luminance)⁻¹. (OrganicEL Material and Display, published by CMC (2001), page 107).

As for the devices of Evaluation Examples 1-12 which were prepared byusing the light-emitting polymer solution compositions containing ionpair, remarkable improvement of life-time was observed, compared withthe devices of Comparative Evaluation Example 1 which was prepared usinga light-emitting polymer solution composition not containing an ionpair. TABLE 1 Initial Adding luminance Half life- amount at 10 mA timeat 10 mA 2000 cd/m² (per resin driving driving conversion life Kindweight %) (cd/m²) (hr) time (hr) Evaluation Compound A 0.1 2200 1.9 2.1Example 1 Evaluation Compound B 0.1 2960 1.8 2.7 Example 2 EvaluationCompound B 0.2 1821 2.4 2.2 Example 3 Evaluation Compound C 0.1 2240 1.41.6 Example 4 Evaluation Compound D 0.1 2620 1.1 1.4 Example 5Evaluation Compound E 0.1 2750 2.3 3.2 Example 6 Evaluation Compound F0.1 2890 1.5 2.2 Example 7 Evaluation Compound G 0.1 2100 1.9 2.0Example 8 Evaluation Compound H 0.2 1640 4.8 3.9 Example 9 EvaluationCompound I 0.2 1690 1.8 1.5 Example 10 Evaluation Compound K 0.1 19903.1 3.1 Example 11 Evaluation Compound L 0.1 1790 2.9 2.6 Example 12Comparative — 0 2760 0.85 1.2 Evaluation Example 1<Preparation 2 of Light-Emitting Polymer Solution Composition>

70:30 (weight ratio) mixture of Light-emitting Polymer 3 andLight-emitting Polymer 4 was dissolved in a mixed solvent oftoluene/ethyl acetate=80/20 (weight ratio) in an amount to be 1.2 wt %,and further an ion pair was mixed in an amount as shown in Table 2 anddissolved. Then, it was filtrated through Teflon (registered trademark)filter having 0.2μ diameter and a coating solution was prepared. As theion pair, those of Synthetic Examples were used. Adding amount of theion pair is shown as the weight part to 100 parts by weight of the wholelight-emitting polymer.

<Preparation of a Device, and Evaluation>

On a glass substrate on which ITO film was formed in a thickness of 150nm by sputtering method, a film was formed by a thickness of 70 nm witha spin coat using a solution (Bayer Co., Baytron) ofpoly(ethylenedioxythiophene)/polystyrene sulfonic acid, and then it wasdried at 200° C. for 10 minutes on a hot plate. Next, a film of about 85nm thicknes was formed by spin-coating at a rotational rate of 1000 rpm,using the prepared coating solution of light-emitting polymer.

Furthermore, after drying this at 90° C. under reduced pressure for 1hour, a polymer LED was fabricated, by depositing 1 nm of LiF as thecathode buffer layer, 5 nm of calcium as the cathode, and subsequently,100 nm of aluminum. Here, all of the vacuum degree at the time ofdeposition were 1 to 9×10⁻⁵ Torr.

By applying a voltage to the resultant device, EL luminescence from alight emitting polymer was observed. Characteristics of the resultantdevice are shown in Table 1.

As the life-time test, luminance was measured about device having a 2mm×2 mm (area 4 mm²) light-emitting part, with conducting a 10 mAconstant current driving.

5000 cd/m² conversion life time is defined as that converted to a lifetime at the time of the initial luminance of 5000 cd/m² driving, withassuming the relation of half life-time∝(initial luminance)⁻¹. (OrganicEL Material and Display, published by CMC (2001), page 107).

As for the devices of Evaluation Examples 13-16 which were prepared byusing the light-emitting polymer solution compositions containing ionpair, remarkable improvement of life-time was observed, compared withthe device of Comparative Evaluation Example 2 which was prepared usinga light-emitting polymer solution composition not containing an ionpair. TABLE 2 Initial Half life Adding luminance time at amount at 10 mA10 mA 5000 cd/m² (per resin driving driving conversion Kind weight %)(cd/m2) (hr) life time (hr) Evaluation Com- 0.1 5830 6.5 7.6 Example 13pound E Evaluation Com- 0.2 4730 10 9.5 Example 14 pound E EvaluationCom- 0.1 6260 2.4 3.0 Example 15 pound M Evaluation Com- 0.1 4420 5.54.9 Example 16 pound N Comparative 0 6070 1.5 1.8 Evaluation Example 2

SYNTHETIC EXAMPLE 28

<Synthesis of Light-Emitting Polymer 5>

2,7-dibromo-9,9-dioctylfluorene (26 g, 0.047 mol),2,7-dibromo-9,9-diisopentylfluorene (5.6 g, 0.012 mol), and2,2′-bipyridyl (22 g, 0.141 mol) were dissolved in dehydratedtetrahydrofuran 1600 mL, and the inside of the system was replaced bynitrogen bubbling. Under nitrogen atmosphere, to this solution,bis(1,5-cyclooctadiene)Ni(0){Ni(COD)₂} (40 g, 0.15 mol) was added, andthe temperature was raised to 60° C., and reacted for 8 hours. After thereaction, the reaction mixture was cooled to room temperature (about 25°C.), added dropwise into a mixed solution of 25% aqueous ammonia 200ml/methanol 1200 ml/ion-exchanged water 1200 ml, and stirred for about30 minutes. The deposited precipitate was filtrated, and air-dried.After being dissolved in toluene 1100 mL, it was filtrated, and thefiltrated solution was added dropwise in methanol 3300 mL, and wasstirred for 30 minutes. The deposited precipitate was filtrated andwashed by methanol 1000 mL, then dried under reduced-pressure for 5hours. The yield of a resultant Light-emitting Polymer 5 was 20 g. Thepolystyrene reduced number average molecular weight and weight averagemolecular weight of Light-emitting Polymer 1 were Mn=4.6×10⁴ andMw=1.1×10⁵, respectively, (mobile-phase: chloroform).

<Preparation of Light-Emitting Polymer Solution Composition>

Light-emitting Polymer 5 was dissolved in toluene be 1.5 wt %, andfurther an onium salt was mixed in an amount as shown in Table 3 anddissolved. Then, it was filtrated through Teflon (registered trademark)filter having 0.29 diameter and a coating solution was prepared. As theonium salt, Rohdorsil photoinitiator PI-2074 prepared by Rohdia wereused. Adding amount of the onium salt is shown as the weight part to 100parts by weight of the whole light-emitting polymer. TABLE 3

Adding Initial Half life amount luminance time 100 cd/m² of at 1 mA at 1mA conversion onium driving driving life time salt UV exposure (cd/m²)(hr) (hr) Evaluation 0.05 Not 124 47 58 Example 17 conducted Evaluation0.05 Conducted 223 24 54 Example 18 Evaluation 0.1 Conducted 93 (78%at >>125 Example 19 135 hr) Evaluation 0.2 Conducted 70 (93% at >>95Example 20 135 hr) Comparative 0 Not 163 2.7 4.4 Evaluation conductedExample 3 Comparative 0 Conducted 256 2.3 5.9 Evaluation Example 4<Preparation of a Device, and Evaluation>

On a glass substrate on which ITO film was formed in a thickness of 150nm by sputtering method, a film was formed by a thickness of 70 nm witha spin coat using a solution (Bayer Co., Baytron) ofpoly(ethylenedioxythiophene)/polystyrene sulfonic acid, and then it wasdried at 200° C. for 10 minutes on a hot plate. Next, a film of about 85nm thicknes was formed by spin-coating at a rotational rate of 1400 rpm,using the prepared coating solution of light-emitting polymer.

In case of conducting UV exposure, under nitrogen atmosphere, UVexposure conducted for 10 seconds, by a high-pressure mercury lamp of 50W/cm² illumination measured by i-line (365 nm).

Furthermore, after drying this at 90° C. under reduced pressure for 1hour, a polymer LED was fabricated, by depositing 1 nm of LiF as thecathode buffer layer, 5 nm of calcium as the cathode, and subsequently,100 nm of aluminum. Here, all of the vacuum degree at the time ofdeposition were 1 to 9×10⁻⁵ Torr.

By applying a voltage to the resultant device, EL luminescence from alight emitting polymer was observed. Characteristics of the resultantdevice are shown in Table 3.

As the life-time test, luminance was measured about device having a 2mm×2 mm (area 4 mm²) light-emitting part, with conducting a 10 mAconstant current driving.

100 cd/m² conversion life time is defined as that converted to a lifetime at the time of the initial luminance of 100 cd/m² driving, withassuming the relation of half life-time∝(initial luminance)⁻¹. (OrganicEL Material and Display, published by CMC (2001), page 107).

As for the devices of Evaluation Examples 17-20 which were prepared byusing the light-emitting polymer solution compositions containing ionpair, remarkable improvement of life-time was observed, compared withthe devices of Comparative Evaluation Examples 3 and 4 which wereprepared using a light-emitting polymer solution composition notcontaining an ion pair.

SYNTHETIC EXAMPLE 29

<Synthesis of triphenylsulfonium tetrakis(pentafluoro phenyl)borate salt(TPSTB)>

In a 100 ml three-necked flask, 0.90 g of lithium tetrakis(pentafluorophenyl)borate, and 10 ml of chloroform were mixed. Then, 10ml aqueous solution of 0.30 g triphenyl sulfonium salt was added, andstirred for 24 hours. After removing the aqueous layer, it washed byion-exchanged water. The chloroform solution was concentrated and dried,and recrystallized from methanol-t-butylmethyl ether, 0.80 g of whitesolid was obtained.

¹H-NMR (300 MHz/CDCl₃): δ (ppm) 7.50, (d, 2H) 7.70, (dd, 2H), 7.83(dd,1H)

¹⁹F-NMR (300 MHz/CDCl₃): d (ppm)-128.85 (d, 2F), −159.28 (dd, 1F),−163.09 (dd, 2F).

SYNTHETIC EXAMPLE 30

<Synthesis of trimethylsulfonium tetrakis(pentafluoro phenyl)borate salt(TMeSTB)>

In a 100 ml three-necked flask, 0.27 g of lithium tetrakis(pentafluorophenyl)borate, and 10 ml of chloroform were mixed. Then, 10ml aqueous solution of 0.10 g triphenyl sulfonium salt was added, andstirred for 21 hours. The deposited solid was filtrated, and washed bychloroform and water. 0.18 g of white solid was obtained.

¹H-NMR (300 MHz/DMSO-d₆) (s, 9H): δ (ppm) 2.90

¹⁹F-NMR (300 MHz/DMSO-d₆): d(ppm)-132.86 (d, 2F), −161.75 (dd, 1F),−166.41 (dd, 2F).

SYNTHETIC EXAMPLE 31

<Synthesis of tetrabutylammonium tetrakis(pentafluoro phenyl)borate salt(N4B)>

Inside of a 50 ml two-necked flask is replaced with nitrogen, 0.15 g oftetrabutylammonium chloride was dissolved in 4.4 ml water, and 0.44 g oflithium[tetrakis(pentafluorobenzene)]borate-ethyl ether complex wasadded. After being dissolved once, then a solid was deposited. The solidwas dissolved by addition of 4.4 ml chloroform. After 5 hours stirring,it was partitioned and the aqueous phase was extracted with 5 mlchloroform twice. After drying with sodium sulfate, the solvent wasdistilled off, and 0.45 g of 1 was obtained.

¹H-NMR (300 MHz, CDCl₃)

δ 3.09-3.03 (8H, m), 1.62-1.51 (8H, m), 1.42-1.30 (8H, m), 0.97 (12H, t)

¹⁹F-NMR (300 MHz, CDCl₃)

δ 14.2, 10.3, −133.1

MS(ESI-positive)

m/z:242

MS(ESI-negative)

m/z:679

EXAMPLE 32

Synthesis of 1′-diphenyl-4,4′-bipyridiniumbistetrakis(pentafluorophenyl)borate

Inside of a 25 ml Schlenk tube was replaced by nitrogen, 57 mg of1,1′-diphenyl-4,4′-bipyridinium dichloride was dissolved in 2.5 ml ofwater, and 250 mg of lithium[tetrakis (pentafluorobenzene)]borate-ethylether complex was added. 2.5 ml of chloroform was added, and it wasstirred for 7 hours. It was partitioned, and the aqueous phase wasfiltrated and washed. The residue and the organic layer were combinedand the solvent was distilled off, and then 129 mg of1,1′-diphenyl-4,4′-bipyridinium bistetrakis(pentafluorophenyl)borate wasobtained.

¹H-NMR (300 MHz, DMSO-d₆)

δ 9.71 (4H, d), 9.07 (4H, d), 7.98 (4H, d), 7.83 to 7.79 (6H, m)

¹⁹F-NMR (300 MHz, DMSO-d₆)

δ −132.8, −161.8, −166.3

SYNTHETIC EXAMPLE 33

(Synthesis of 4-{4-(dimethylamino)Styryl}-N-methyl pyridiniumtetrakis(pentafluorophenyl)borate)

Inside of a 25 ml Schlenk tube was replaced by nitrogen, 113 mg of4-(4-(Dimethylamino)styryl)-N-methylpyridinium iodide was suspended in2.5 ml water, and 250 mg of lithium[tetrakis (pentafluorobenzene)]boratewas added. 2.5 ml of chloroform was added, and it was stirred for 7hours. It was partitioned, and the aqueous phase was filtrated andwashed. The residue and the organic layer were combined together and thesolvent was distilled off, and then 91 mg of4-{4-(dimethylamino)styryl}-N-methylpyridiniumtetrakis(pentafluorophenyl)borate was obtained.

¹H-NMR (300 MHz, DMSO-d₆)

δ 8.69 (2H, d), 8.05 (2H, d), 7.91 (1H, d), 7.60 (2H, d), 7.17 (1H, d),6.79 (2H, d), 4.18 (3H, s), 3.03 (6H, s)

¹⁹F-NMR (300 MHz, DMSO-d₆)

δ −132.8, −161.8, −166.3

SYNTHETIC EXAMPLE 34

(Synthesis of transformer-4-{2-(1-ferrocenyl)vinyl}-1-methylpyridiniumtetrakis(pentafluorophenyl)borate)

Inside of a 25 ml Schlenk tube was replaced by nitrogen, 130 mg oftrans-4-[2-(1-Ferrocenyl)vinyl]-1-methylpyridinium iodide was suspendedin 2.5 ml water, and 250 mg oflithium[tetrakis(pentafluorobenzene)]borate was added. 2.5 ml ofchloroform was added, and it was stirred for 7 hours. It waspartitioned, and the aqueous phase was filtrated and washed. The residueand the organic layer were combined together and the solvent wasdistilled off, and then 167 mg oftrans-4-{2-(1-ferrocenyl)vinyl}-1-methypyridinium tetrakispentafluorophenyl borate was obtained.

¹H-NMR (300 MHz, DMSO-d₆)

δ 8.73 (2H, d), 8.06 (2H, d), 7.89 (1H, d), 6.97 (2H, d), 4.75 (2H, s),4.60 (2H, s), 4.23 (5H, s), 4.19 (3H, s)

¹⁹F-NMR (300 MHz, DMSO-d₆)

δ−132.6, −161.8, −166.1

SYNTHETIC EXAMPLE 35

<Synthesis of tetradodecylammonium tetrakis(pentafluorophenyl)borate>

Inside of a 25 ml Schlenk tube was replaced by nitrogen, 225 mg oftetradodecylammonium chloride was dissolved in 2.5 ml water, and 250 mgof lithium[tetrakis(pentafluorobenzene)]borate was added. 2.5 ml ofchloroform was added, and it was stirred for 7 hours. It waspartitioned, and the aqueous phase was filtrated and extracted withchloroform, and then the solvent was distilled off. 407 mg oftetradodecylammonium tetrakis(pentafluorophenyl)borate was obtained.

¹H-NMR (300 MHz, CDCl₃)

δ 3.02 (8H, br), 1.56 (8H, br), 1.29 to 1.23 (44H, m), 0.87 (12H, t)

¹⁹F-NMR (300 MHz, CDCl₃)

δ −132.2, −162.5, −166.5

<Preparation of Light-Emitting Polymer Solution Composition>

Light-emitting Polymer 5 was dissolved in toluene in an amount to be 1.5wt %, and further a metal salt or an onium, as additives, was mixed inan amount as shown in Table 4 and dissolved. Then, it was filtratedthrough Teflon (registered trademark) filter having 0.2μ diameter and acoating solution was prepared. As the metal salt or the onium, those ofSynthetic Examples and commercially available reagents shown below wereused. Adding amount of the metal salt or the onium is shown as theweight part to 100 parts by weight of the whole light-emitting polymer.

LiB: Lithium tetrakis(pentafluorophenyl)borate-ethylether complex(product by Tokyo-Kasei)

AB: N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (product bySTREM CHEMICALS)

TB: Trityl tetrakis(pentafluorophenyl)borate (Product by STREMCHEMICALS) TABLE 4 Initial Half life 100 luminance time at cd/m² Addingamount at 10 mA 10 mA conversion (per resin driving driving life timeKind weight %) UV exposure (cd/m²) (hr) (hr) Evaluation TPSTB 0.2 not 4429 12.8 Example 21 conducted Evaluation TPSTB 0.2 conducted 55 15 8.3Example 22 Evaluation TMeSTB 0.2 not 23 112 25.8 Example 23 conductedEvaluation N4B 0.2 not 38 10 3.8 Example 24 conducted Evaluation LiB 0.2not 63 65 41.0 Example 25 conducted Evaluation AB 0.2 conducted 49 5426.5 Example 26 Evaluation TB 0.2 conducted 34 85 28.9 Example 27Evaluation PI2074 0.2 not 54 70 37.8 Example 28 conducted EvaluationPI2074 0.2 conducted 48 29 13.9 Example 29 Comparative — 0 not 85 1.51.3 Evaluation conducted Example 5 Comparative — 0

113 1.3 1.5 Evaluation Example 6<Preparation of a Device, and Evaluation>

On a glass substrate on which ITO film was formed in a thickness of 150nm by sputtering method, a film was formed by a thickness of 50 nm witha spin coat using a solution (Bayer Co., Baytron) ofpoly(ethylenedioxythiophene)/polystyrene sulfonic acid, and then it wasdried at 200° C. for 10 minutes on a hot plate. Next, a film of about 85nm thicknes was formed by spin-coating at a rotational rate of 1400 rpm,using the prepared coating solution of light-emitting polymer.

In case of conducting UV exposure, under nitrogen atmosphere, UVexposure conducted for 10 seconds, by a high-pressure mercury lamp of 50W/cm² illumination measured by i-line (365 nm).

Furthermore, after drying this at 90° C. under reduced pressure for 1hour, a polymer LED was fabricated, by depositing 1 nm of LiF as thecathode buffer layer, 5 nm of calcium as the cathode, and subsequently,100 nm of aluminum. Here, all of the vacuum degree at the time ofdeposition were 1 to 9×10⁻⁵ Torr.

By applying a voltage to the resultant device, EL luminescence from alight emitting polymer was observed. Characteristics of the resultantdevice are shown in Table 3.

As the life-time test, luminance was measured about device having a 2mm×2 mm (area 4 mm²) light-emitting part, with conducting a 10 mAconstant current driving.

100 cd/m² conversion life time is defined as that converted to a lifetime at the time of the initial luminance of 100 cd/m² driving, withassuming the relation of half life-time∝(initial luminance)⁻¹. (OrganicEL Material and Display, published by CMC (2001), page 107).

As for the devices of Evaluation Examples 21-29 which were prepared byusing the light-emitting polymer solution compositions containing ionpair, remarkable improvement of life-time was observed, compared withthe devices of Comparative Evaluation Examples 5 and 6 which wereprepared using a light-emitting polymer solution composition notcontaining an ion pair.

SYNTHETIC EXAMPLE 36

(Synthesis of tri(4-t-butylphenylsulfonium)tetrakis(pentafluorophenyl)borate salt (TTBPSTB))

Inside of a 200 ml four-necked flask was replaced with nitrogen, 0.581 gof tri(4-t-butylphenylsulfonium)trifluoromethane sulfonate, and 0.834 gof lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex, 20 mlof ion-exchanged water, and 60 ml of diethyl ether were charged. Afterequipping with stirring blade, thermometer, and condenser, it wasreacted at 21-23° C. for 16 hours. After the reaction, the contents ofthe flask were put into a 200 ml separatory funnel, and the aqueouslayer was removed. Next, the ether layer was washed 3 times by 30 ml ofion-exchanged water. The ether layer was put in a 200 ml Erlenmeyerflask, anhydrous sodium sulfate was added to dehydrate, and anhydroussodium sulfate was filtrated off. The ether layer was condensed byevaporator at room temperature, and dried until it became to a constantweight by a vacuum pump at 70-75° C. 1.04 g of a compound (TTBPSTB) wasobtained.

¹H-NMR (270 MHz, DMSO-D₆)

δ 7.78 (12H,m), 1.31 (27H, s)

<Preparation of Light-Emitting Polymer Solution Composition>

70:30 (weight ratio) mixture of Light-emitting Polymer 3 andLight-emitting Polymer 4 was dissolved in a mixed solvent oftoluene/ethyl acetate=80/20 (weight ratio) in an amount to be 1.2 wt %,and further an ion pair was mixed in an amount as shown in Table 5 anddissolved. Then, it was filtrated through Teflon (registered trademark)filter having 0.2μ diameter and a coating solution was prepared. As theion pair, those of Synthetic Examples were used. Adding amount of theion pair is shown as the weight part to 100 parts by weight of the wholelight-emitting polymer.

<Preparation of a Device, and Evaluation>

On a glass substrate on which ITO film was formed in a thickness of 150nm by sputtering method, a film was formed by a thickness of 50 nm witha spin coat using a solution (Bayer Co., Baytron) ofpoly(ethylenedioxythiophene)/polystyrene sulfonic acid, and then it wasdried at 200° C. for 10 minutes on a hot plate. Next, a film of about 85nm thicknes was formed by spin-coating at a rotational rate of 1000 rpm,using the prepared coating solution of light-emitting polymer.

Furthermore, after drying this at 90 under reduced pressure for 1 hour,a polymer LED was fabricated, by depositing 1 nm of LiF as the cathodebuffer layer, 5 nm of calcium as the cathode, and subsequently, 100 nmof aluminum. Here, all of the vacuum degree at the time of depositionwere 1 to 9×10⁻⁵ Torr.

By applying a voltage to the resultant device, EL luminescence from alight emitting polymer was observed. Characteristics of the resultantdevice are shown in Table 3.

As the life-time test, luminance was measured about device having a 2mm×2 mm (area 4 mm²) light-emitting part, with conducting a 10 mAconstant current driving.

5000 cd/m² conversion life time is defined as that converted to a lifetime at the time of the initial luminance of 5000 cd/m² driving, withassuming the relation of half life-time∝(initial luminance)⁻¹. (OrganicEL Material and Display, published by CMC (2001), page 107).

As for the devices of Evaluation Example 30 which was prepared by usingthe light-emitting polymer solution compositions containing ion pair,remarkable improvement of life-time was observed, compared with thedevices of Comparative Evaluation Example 7 which was prepared using alight-emitting polymer solution composition not containing an ion pair.TABLE 5 Initial lumi- Half nance reduction Adding at time at 5000 cd/m²amount 10 mA 10 mA conversion (weight % driving driving life Kind perresin) (cd/m²) (hr) time (hr) Evaluation TTBPSTB 0.2 3210 9 5.8 Example30 Comparative — 0 6070 1.5 1.8 Evaluation Example 7

Life time of a light-emitting device can be lengthened by using a lightemitting layer containing the light-emitting polymer composition of thepresent invention. Therefore, the polymer LED which used thelight-emitting polymer composition of the present invention can bepreferably used for apparatus, such as a curved or flat light source fora liquid crystal display as a back light, a segment type display, a dotmatrix flat-panel display, etc.

1. A light-emitting polymer composition comprising a light-emitting polymer and an ion pair, and the negative ion of the ion pair is represented by below formula (1a), (1b), (2) or (3),

(wherein, Y¹ represents a group 13 atom; Ar¹ represents an aryl group having an electron-withdrawing group, or a monovalent heterocyclic group having an electron-withdrawing group; Q¹ represents an oxygen atom or a direct bond; X¹ represent a halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, substituted amino group, amide group, acid imide group, acyloxy group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, cyano group, or nitro group; a represents an integer of 1-3, k represents an integer of 1-4, V¹ represents a group 16 atom, divalent aliphatic hydrocarbon group, divalent aromatic hydrocarbon group, bidentate heterocyclic group, —C≡N—, —N═N═N—, or a direct bond; b represents an integer of 2-6; and Z¹ represents -M′(=O)p- (wherein, M′ represents an atom of group 3, group 4, group 5, group 6, group 7, group 8, group 9, group 10, group 11, group 12, group 13, group 14, group 15, group 16, or group 17; and p represents an integer of 0-2), or Z¹ represents a b-valent aliphatic hydrocarbon group, a b-valent aromatic hydrocarbon group, a bidentate heterocyclic group, —C≡N—, —N═N═N—, —NH—, —NH₂—, —OH—, or a direct bond. However, b=2 when Z¹ is —C≡N—, —N═N═N—, —NH—, —NH₂—, or —OH—; Z¹ and V¹ are different from each other, and when Q¹ and Ar¹ exist in plural, they may be the same or different from each other; a plurality of V¹ is may be the same or different; and c represents an integer of 1-6),

(wherein, Y² represents a group 13 atom; Ar² represents an aryl group having an electron-withdrawing group, or a monovalent heterocyclic group having an electron-withdrawing group; Q² represents an oxygen atom or a direct bond; X² represent a halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, substituted silyl oxy group, substituted silylthio group, substituted silylamino group, substituted amino group, amide group, acid imide group, acyloxy group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, cyano group, or nitro group; d and d′ each independently represent 1 or 2; V² represents a group 16 atom, divalent aliphatic hydrocarbon group, divalent aromatic hydrocarbon group, bidentate heterocyclic group, —C≡N— or —N═N—; a plurality of Y², Ar², Q² and V² may be the same or different; when X² exists in plural, they may be the same or different; and e represents an integer of 1-6),

(wherein, Y³ represents a group 13 atom; Ar³ represents an aryl group having an electron-withdrawing group, or a monovalent heterocyclic group having an electron-withdrawing group; Q³ represents an oxygen atom or a direct bond; V³ represents a group 16 atom, divalent aliphatic hydrocarbon group, divalent aromatic hydrocarbon group, bidentate heterocyclic group, —C≡N—, or —N═N—; a plurality of Y³, Ar³, Q³ and V³ espectively may be the same or different; and f represents an integer of 1-6).
 2. A light-emitting polymer composition according to claim 1, wherein, Ar¹ in the above formula (1a) and (1b), Ar² in the above formula (2), and Ar³ in the above formula (3) are perfluoroaryl groups.
 3. A light-emitting polymer composition according to claim 1, wherein a is 2 or 3 in the above formula (1a).
 4. A light-emitting polymer composition according to claim 1, wherein k is 3 or more in the above formula (1b).
 5. A light-emitting polymer composition according to claim 1, wherein the above formula (1b) is the below formula (6), [B(Ar⁴)₄]⁻  (6) (wherein, Ar⁴ represents a phenyl group substituted with 2 or more of those selected from fluorine and trifluoromethyl group; and Ar⁴ may be mutually the same or different).
 6. A light-emitting polymer composition according to claim 1, wherein, in the above formula (1a), Z¹ or V¹ is —C≡N—.
 7. A light-emitting polymer composition according to claim 1, wherein the negative ion of the above formula (1a) is represented by the below formula (5-1) or (5-2), [(C₆F₅)₃B—C≡N—B(C₆F₅)₃]⁻  (5-1) [M{C≡N—B(C₆F₅)₃}₄]²⁻  (5-2) (wherein, M represents a nickel atom or a palladium atom).
 8. A light-emitting polymer composition according to claim 1, wherein the positive ion of the ion pair is a hydrogen ion, a metal cation, or carbocation; or an onium of the element selected from a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, a chlorine atom, a selenium atom, a bromine atom, a tellurium atom, and an iodine atom.
 9. A light-emitting polymer composition according to claim 8, wherein the onium of nitrogen atom is a divalent onium represented by the below formula (10),

(wherein, R³ and R⁴ each independently represent an alkyl group, alkyloxy group, aryl group, aryloxy group, arylalkyl group, arylalkyloxy group, acyl group, acyloxy group, monovalent heterocyclic group, or hetero aryloxy group; R⁵ and R⁶ each independently represent a halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, substituted amino group, amide group, acidimide group, acyloxy group, monovalent heterocyclic group, hetero aryloxy group, hetero arylthio group, acyl group, imine residue, substituted silyl group, alkyloxy carbonyl group, aryloxy carbonyl group, arylalkyloxy carbonyl group, heteroaryloxy carbonyl group, carboxyl group, cyano group, or nitro group; T represents a direct bond, divalent aliphatic hydrocarbon group, divalent aromatic hydrocarbon group, alkenylene group, ethynylene group, or a divalent heterocyclic group; i and j each independently represent an integer of 0 to 4; when two or more R⁵ and R⁶ respectively exist, they may be the same or different).
 10. A light-emitting polymer composition according to claim 1, wherein the light-emitting polymer comprises the repeating unit represented by the below formula (4),

(wherein, A represents an atom or an atomic group for forming the 5 membered ring or 6 membered ring together with 4 carbon atoms on two benzene rings of the formula; R^(4a), R^(4b), R^(4c), R^(5a), R^(5b), and R^(5c) each independently represent a hydrogen atom, a halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acidimide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, cyano group, nitro group, monovalent heterocyclic group, heteroaryloxy group, hetero arylthio group, alkyloxy carbonyl group, aryloxy carbonyl group, arylalkyloxy carbonyl group, heteroaryloxy carbonyl group, or carboxyl group; R^(4b) and R^(4c), and R^(5b) and R^(5c) may respectively form a ring, together.).
 11. A light-emitting polymer composition according to claim 1, wherein the content of the ion pair is 0.001-10 parts by weight based on 100 parts by weight of the light-emitting polymer.
 12. A light-emitting polymer solution composition wherein the light-emitting polymer composition according to claim 1 further contains a solvent.
 13. A polymer light-emitting device comprising a light emitting layer between the electrodes consisting of an anode and a cathode, wherein the light emitting layer contains the light-emitting polymer composition according to claim
 1. 14. A polymer light-emitting device comprising a light emitting layer between the electrodes consisting of an anode and a cathode, wherein the light emitting layer is formed using the light-emitting polymer solution composition of claim
 12. 15. A polymer light-emitting device according to claim 13, wherein the device is manufactured by being heat-treated at the temperature of 50° C. or more, after forming the light emitting layer.
 16. An ion pair wherein the negative ion is represented by the below formula (5-1), and the positive ion is a pyridinium cation, phosphonium cation, or iodonium cation, [(C₆F₅)₃B—C≡N—B(C₆F₅)₃]⁻  (5-1)
 17. An ion pair wherein the negative ion is represented by the below formula (5-2), and the positive ion is a pyridinium cation, quarternary ammonium cation, a phosphonium cation, oxonium cation, sulfonium cation, or iodonium cation. [M{C≡N—B(C₆F₅)₃}₄]²⁻  (5-2) (wherein, M represents a nickel atom or a palladium atom.).
 18. An ion pair represented by the below formula (12),

(wherein, R³, R⁴, R⁵, R⁶, and T represent the same meaning as the above.) 